EP1060149A1 - Corps de cordierite a faible coefficient de dilatation thermique, ayant une repartition etroite de la taille des pores, et procede de fabrication de ces corps - Google Patents
Corps de cordierite a faible coefficient de dilatation thermique, ayant une repartition etroite de la taille des pores, et procede de fabrication de ces corpsInfo
- Publication number
- EP1060149A1 EP1060149A1 EP99906790A EP99906790A EP1060149A1 EP 1060149 A1 EP1060149 A1 EP 1060149A1 EP 99906790 A EP99906790 A EP 99906790A EP 99906790 A EP99906790 A EP 99906790A EP 1060149 A1 EP1060149 A1 EP 1060149A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- less
- micrometers
- raw materials
- particle diameter
- kaolin
- 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- Withdrawn
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
- C04B35/01—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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
- C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
Definitions
- This invention relates to cordierite bodies having a unique combination of low coefficient of thermal expansion (CTE) and narrow pore size distribution. This is accomplished by use of selected combinations of raw materials and firing schedules.
- CTE coefficient of thermal expansion
- the bodies are honeycomb structures that find use as substrates for catalytic reactions, and for filtration applications.
- Cordierite bodies having honeycomb structures are especially suited for but not limited to use as substrates for catalysts for converting automotive exhaust, for example, or as diesel particulate filters or as regenerator cores.
- Use of cordierite is favorable in these applications because of its good thermal shock resistance.
- the thermal shock resistance is inversely proportional to the coefficient of thermal expansion (CTE). That is, honeycombs with low thermal expansion have good thermal shock resistance and can survive the wide temperature fluctuations that are encountered in the application.
- a cordierite body of CTE at 25-800°C of ⁇ 4 x 10 "7 C " ⁇ with at least 85% of its total porosity having a mean pore diameter of 0.5-5.0 micrometers.
- a cordierite body of CTE at 25-800°C of >4-6 x W '7 C ' a total porosity of at least 30 vol%, at least
- a method of making the above-described cordierite bodies that involves intimately blending the raw materials of talc, an Al 2 O 3 -forming source, and one or more of kaolin, calcined kaolin, and silica, and optionally spinel with vehicle and forming aids into a plastic mixture.
- the mean particle diameter of the talc is ⁇ 3.0 micrometers, that of the Al 2 O 3 -forming source is ⁇ 2.0 micrometers.
- the kaolin if present, is ⁇ 35 wt% of raw materials when particle diameter is ⁇ 2.0 micrometers.
- a green body is formed, which is dried and fired at 1370°C-1435°C.
- the heating rate from 1150°C-1275°C is >200°C/hr.
- the Al 2 O 3 -forming source is ⁇ 20 wt% of the raw materials
- dispersible high surface area Al 2 O 3 -forming source having a mean particle diameter of ⁇ 0.3 micrometers is ⁇ 5.0 wt% of the raw materials
- the mean particle diameter of the kaolin is ⁇ 2.0 micrometers
- 1150°C-1275°C is >50°C/hr and ⁇ 600°C/hr.
- the Al 2 O 3 -forming source is less than 20 wt% of the raw materials, and dispersible Al 2 ⁇ 3 -forming source having particle diameter of ⁇ 0.3 micrometers is >5.0 wt% of the raw materials, and the mean particle diameter of the kaolin is ⁇ 2.0 micrometers, the heating rate from 1150°C-1275°C is >50°C/hr.
- the heating rate from 1150°C-1275°C is ⁇ 600°C/hr and >30°C/hr.
- This invention relates to cordierite bodies having a unique combination of low thermal expansion or CTE measured at 25-800°C, and narrow pore size distribution.
- CTEs are the mean expansions from 25-800°C measured by dilatometry. In honeycombs it is the mean expansion along the direction parallel to the length of the open channels. Unless otherwise specified particle size is expressed as mean particle diameter.
- Particle size is measured by a sedimentation technique.
- Porosity is total porosity measured by mercury porosimetry and is expressed as volume percent.
- the success of the present invention in obtaining low CTE and very narrow pore size distributions between 0.5 and 5.0 micrometers is based upon the use of fine talc in combination with certain raw materials and firing schedules to maintain low CTE.
- the use of fine talc enables the attainment of very high fractions of porosity between 0.5 and 5.0 micrometers.
- finer talcs have a tendency to result in a body with a higher CTE due to reduced microcracking.
- the -4- other raw materials must be selectively chosen and, for some raw material combinations, certain restrictions must be placed upon the heating rates during firing.
- the raw materials that are utilized are talc, an Al 2 O 3 -forming source, one or more of the components of kaolin, calcined kaolin, and silica.
- spinel can be a raw material.
- the talc must have a mean particle diameter of no greater than 3.0 micrometers.
- Al 2 O 3 -forming source is meant Al 2 O 3 itself or other material having low water solubility which when fired converts to Al 2 O 3 .
- Al 2 O 3 -forming components include alumina, Al(OH) 3 (also known as aluminum trihydrate or the mineral gibbsite), or aluminum oxide hydroxide (also known as aluminum monohydrate or the mineral boehmite or pseudo-boehmite.
- Dispersible high surface area Al 2 O 3 -forming component or source can be provided as the powder or as a sol.
- dispersible is meant that the agglomerates of very fine particles can be broken up and dispersed into the constituent particles having a mean particle diameter of less than about 0.3 micrometers.
- high surface area is meant a surface area greater than about 10m /g and preferably greater than about 40m /g.
- Such powders can include boehmite, pseudoboehmite, gamma-phase alumina, delta-phase alumina, or other so-called transition aluminas.
- the Al 2 O 3 -forming source must have a mean particle diameter of no greater than 2.0 micrometers, and preferably a specific surface area greater than about 5 m 2 /g. It is preferred that the amount of Al 2 O 3 -forming source be at least about 20% by weight of the raw materials to allow the broadest range in heating rates and still obtain low CTE bodies.
- the mean particle diameter of the kaolin can range between about 0.2 and 10 micrometers. However, if the mean particle size is less than about 2 micrometers, the amount of such kaolin used must be less than about 35 wt.% of the total raw material charge.
- the balance of the Al 2 O 3 required to form cordierite is supplied by calcined kaolin or an Al 2 O 3 -forming source, and the balance of the SiO 2 being supplied by calcined kaolin or silica powder. It is preferred that the amount of -5-
- Al 2 O 3 -forming source provided as a dispersible high surface area Al 2 O 3 -forming component be not less than about 5% by weight of the raw material charge.
- the raw materials are blended with vehicle and forming aids that impart plastic formability and green strength to the raw materials when they are shaped into a body.
- the extrusion aids are most typically cellulose ether organic binder, and a lubricant such as sodium ammonium or diglycol stearate, although the invention is not limited to these.
- the organic binder contributes to the plasticity of the mixture for shaping into a body.
- the plasticizing organic binder according to the present invention refers to cellulose ether binders.
- Some typical organic binders according to the present invention are methylcellulose, ethylhydroxy ethylcellulose, hydroxybutyl methylcellulose, hydroxymethylcellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, hydroxybutylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium carboxy methylcellulose, and mixtures thereof.
- Methylcellulose and/or methylcellulose derivatives are especially suited as organic binders in the practice of the present invention with methylcellulose, hydroxypropyl methylcellulose, or combinations of these being preferred.
- Methocel A4M is a methylcellulose
- Methocel F4M, F240, and K75M are hydroxypropyl methylcellulose.
- the organic binder content is typically is about 3% to 6%, based on the raw material.
- the vehicle can be inorganic, i.e. consisting largely of water, which is typically but not exclusively about 28% to 46%; or it can be organic.
- water is preferred, although evaporable organic liquids such as lower alkanols can be wholly or partly substituted as desired.
- the weight percents of the organic binder, vehicle and other additives are calculated as superadditions with respect to the raw materials.
- the mixture is then formed into a green body.
- the preferred forming method is by extrusion through a die. Extrusion can be done by using a hydraulic ram extrusion press, or a two stage de-airing single auger extruder, or a twin screw mixer with a die assembly attached to the discharge end. In the latter, the proper screw elements are -6- chosen according to material and other process conditions in order to build up sufficient pressure to force the batch material through the die.
- the bodies according to the present invention can have any convenient size and shape. However, the process is especially suited to production of cellular monolith bodies such as honeycombs. Cellular bodies find use in a number of applications such as catalyst carriers, filters such as diesel particulate filters, molten metal filters, regenerator cores, etc.
- honeycomb cell densities range from 235 cells/cm 2 (about 1500 cells/in 2 ) to 15 cells/cm 2 (about 100 cells/in 2 ).
- Wall (web) thicknesses range typically from about 0.07 to about 0.6 mm (about 3 to about 25 mils).
- the external size and shape of the body is controlled by the application, e.g. in automotive applications by engine size and space available for mounting, etc.
- This invention is especially advantageous for honeycombs having very thin walls, e.g. ⁇ .13 mm (5 mils).
- Thinner walled honeycombs can be made e.g. .025-.1 mm (1-4 mils) for some of the inventive mixtures especially those that contain clay, alumina, and a talc all of which have a mean particle size of ⁇ 3 micrometers in diameter.
- the green body is then dried according to conventional procedures for green cordierite bodies such as e.g. oven or dielectric drying.
- the dried body is then fired at a temperature of about 1370°C to 1435°C. Depending on the raw material combination, the firing conditions will vary.
- 1150°C and 1275°C is greater than about 200°C/hr to yield the microstructure required for microcracking and low CTE.
- the mean particle diameter of the talc is not less than about 2.0 micrometers, and the amount of Al 2 O 3 -forming source is less than about 20% by weight of the raw materials, and dispersible high surface area Al 2 O 3 -forming source having a mean -7- particle diameter of less than about 0.3 micrometers, if present, constitutes less than about 5.0% by weight of the raw materials, and the mean particle diameter of the kaolin is less than about 2.0 micrometers
- the heating rate between 1150°C and 1275°C is greater than about 50°C/hr and is less than about 600°C/hr.
- the heating rate between 1150°C and 1275°C is greater than about 50°C/hr.
- the heating rate between 1150°C and 1275°C is less than about 600°C/hr and greater than about 30°C/hr.
- the fired body is then cooled to room temperature in as short a time as is practical.
- the cordierite bodies of the present invention are characterized by either (1) a mean coefficient of thermal expansion at 25-800°C of ⁇ 4 x 10 "7 C " '; or (2) a mean coefficient of thermal expansion of >4 x 10 "7 C " ' but ⁇ 6 x 10 "7 C " ', and a total porosity not less than about 30% by volume.
- the total porosity can have any value but is preferably greater than about 18%. In all cases, at least about 85% of the total porosity lies between about 0.5 micrometers and 5.0 micrometers.
- the porous microcracked bodies of the present invention find use as catalytic substrates because the pore size distribution is advantageous for picking up and holding a washcoat.
- the methods of the present invention are especially suitable for manufacture of thin-walled .152 mm ( ⁇ 0.006 inches) and ultra thin walled .102 mm ( ⁇ 0.004 inches) honeycomb bodies of high cell density. Additionally, the porosities and pore size distributions of bodies prepared by the inventive methods are much less sensitive to changes in heating rates during firing than for bodies prepared by conventional methods involving use of coarser talcs. It is believed that these properties should result in less variability in washcoat loading for substrates fired in various locations within a kiln. The narrow pore size distribution can also be useful in certain filtration applications. -8- To more fully illustrate the invention, the following non-limiting examples are presented. All parts, portions, and percentages are on a weight basis unless otherwise stated.
- raw materials were dry blended together with about 3-6% methylcellulose binder and 0.5-1.0% sodium stearate lubricant, and then mixed with about 30-46% water in a stainless steel muller for about 20 minutes.
- the resulting plasticized mixture was subsequently extruded as a honeycomb body having about 62 cells/cm 2 (about 400 cells/in 2 ) and wall thicknesses of about .152 mm (about 0.006 inches).
- the extrudates were wrapped in aluminum foil and dried at about 85°C for about 72 hours.
- Honeycombs were cut to about 10.16 cm (4 inch) lengths and placed on coarse alumina sand on an alumina or cordierite pallet in an electric kiln.
- Examples 1-3 show that the combination of 1.6 micrometer talc, 0.4 micrometer alpha alumina, and 4.5 micrometer crystalline silica yield inventive bodies with low CTE, high total porosity, and more than 85% of the total porosity having a pore size between 0.5 and 5.0 micrometers when fired at a wide range of heating rates.
- Comparative examples 4-6 demonstrate that when the mean particle size of the talc is increased to 6.1 micrometers, in combination with 0.4 micrometer alpha-alumina and 4.5 micrometer crystalline silica, the median pore size increases and the pore size distribution becomes much broader, so that the amount of porosity between 0.5 and 5.0 micrometers is less than 85% of the total porosity.
- Inventive examples 7 and 8 show that a mixture of fine talc having a mean particle size of 1.6 micrometers in combination with a fine kaolin, fine alumina, and calcined kaolin yields CTEs between 4 and 6 x 10 "7o C " ' with total porosities greater than 30% and very narrow pore size distributions such that more than 85% of the total porosity lies between 0.5 and 5.0 micrometers when heated from 1150°C to 1275°C at a rate between 250 and 600°C/hr.
- Examples 9 to 11 illustrate that this combination of raw materials yields CTEs less than 4 x 10 "7o C " ' with greater than 85% of the total porosity lying between 0.5 and 5.0 micrometers when heated at more than 600°C/hr between -9-
- Comparative examples 12 to 14 show that when bodies comprised of these raw materials are heated at less than 250°C/hr, CTEs exceed 6 x lO ' ⁇ C "1 and are therefore non-inventive.
- Inventive examples 15 and 16 demonstrate that a fine talc having a mean particle size of about 2.2 micrometers can be used in combination with a fine kaolin, calcined kaolin, and fine alumina when the 1150-1275°C heating rate is greater than about 50°C/hr but less than about 600°C/hr.
- Comparative example 17 shows that the CTE is greater than 6 x lO ' ⁇ C "1 when the heating rate is less than 50°C/hr from 1150-1275°C.
- Comparative examples 18 and 19 illustrate that when the heating rate between 1150 and 1275°C is faster than about 500°C/hr, the porosity is excessively coarsened, and the percent of total porosity between 0.5 and 5.0 micrometers is less than 85%.
- Comparative examples 20 and 21 demonstrate than when a 3.4 micrometer talc is used in combination with fine kaolin, fine alumina, and calcined kaolin, the mean pore size is coarsened so that the porosity between 0.5 and 5.0 micrometers is less than 85% of the total porosity.
- Comparative example 22 shows that when a 4.2 micrometer talc is used in combination with fine kaolin, fine alumina, and calcined kaolin and is fired at a heating rate slower than 150°C/hr between 1150 and 1275°C, a narrow pore size distribution is obtained, but the CTE is increased to more than 6 x 10 "7o C " ⁇ Comparative examples 23 and 24 show that when this raw material combination is fired at greater than 150°C/hr between 1150 and 1275°C so as to maintain a CTE less than 6 x lO ⁇ C "1 , the mean pore size is coarsened so that the percent of total porosity between 0.5 and 5.0 micrometers is less than 85%.
- Examples 25-30 demonstrate that the partial replacement of 0.4 micrometer alpha- alumina with at least 5% boehmite having a surface area of about 180 m 2 /g and a fine dispersed particle size of about 0.125 micrometers, in combination with a 1.6 micrometer talc, a 0.9 micrometer kaolin, and calcined kaolin, yields bodies having a CTE less than 4 x 10 "7o C " ', and a porosity between 0.5 and 5.0 micrometers that is more than 85% of the total porosity when such bodies are heated at greater than 50°C/hr between 1150 and 1275°C.
- this boehmite to the raw material combination of fine talc, fine kaolin, calcined kaolin, and alpha-alumina allows the use -10- of slower firing rates while maintaining the desired combination of low CTE and narrow pore size distribution.
- Inventive examples 31 and 32 demonstrate that low CTE bodies with very narrow pore size distributions and total porosities not less than 30% are obtained for raw material combinations of 1.6 micrometer talc and a coarser 7.4 micrometer kaolin with
- Comparative example 33 illustrates that CTEs become greater than 6 x lO ' ⁇ C "1 when the heating rate is less than about 30°C/hr between 1150 and 1275°C. Comparative examples 34 and 35 show that when heating rates exceed about 600°C/hr, the mean pore size is coarsened so that the porosity between 0.5 and 5.0 micrometers is no longer at least 85% of the total porosity.
- Comparative examples 36-38 demonstrate that the use of a coarse 4.5 micrometer alpha-alumina powder in combination with fine talc, fine kaolin, and calcined kaolin results in a CTE greater than 6 x lO ' ⁇ C "1 for either slow or fast heating rates.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Catalysts (AREA)
- Filtering Materials (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7584698P | 1998-02-25 | 1998-02-25 | |
US75846P | 1998-02-25 | ||
PCT/US1999/002641 WO1999043629A1 (fr) | 1998-02-25 | 1999-02-09 | Corps de cordierite a faible coefficient de dilatation thermique, ayant une repartition etroite de la taille des pores, et procede de fabrication de ces corps |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1060149A1 true EP1060149A1 (fr) | 2000-12-20 |
EP1060149A4 EP1060149A4 (fr) | 2002-07-17 |
Family
ID=22128355
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99906790A Withdrawn EP1060149A4 (fr) | 1998-02-25 | 1999-02-09 | Corps de cordierite a faible coefficient de dilatation thermique, ayant une repartition etroite de la taille des pores, et procede de fabrication de ces corps |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1060149A4 (fr) |
JP (1) | JP2002504476A (fr) |
CN (1) | CN1287546A (fr) |
WO (1) | WO1999043629A1 (fr) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6087281A (en) * | 1998-02-25 | 2000-07-11 | Corning Incorporated | Low CTE cordierite bodies with narrow pore size distribution and method of making same |
CN1189418C (zh) * | 1998-12-07 | 2005-02-16 | 康宁股份有限公司 | 特低热膨胀堇青石结构体的制造方法 |
BR0011456A (pt) * | 1999-06-11 | 2002-03-19 | Corning Inc | Corpo de cordierita de alta porosidade, alta resistência, baixa expansão, e método |
JP3756721B2 (ja) * | 2000-03-24 | 2006-03-15 | 日本碍子株式会社 | 排ガス浄化用フィルター |
US20030041730A1 (en) * | 2001-08-30 | 2003-03-06 | Beall Douglas M. | Honeycomb with varying channel size |
US7520911B2 (en) | 2005-11-30 | 2009-04-21 | Corning Incorporated | Porous cordierite ceramic honeycomb article with improved strength and method of manufacturing same |
EP2262747B1 (fr) * | 2008-02-29 | 2013-06-05 | Corning Incorporated | Matériau perméable et des articles fabriqués à partir de ce matériau |
CN102249656A (zh) * | 2011-05-31 | 2011-11-23 | 宜兴王子制陶有限公司 | 一种薄壁低膨胀堇青石蜂窝陶瓷的制备方法 |
EP2574391A1 (fr) | 2011-09-15 | 2013-04-03 | NGK Insulators, Ltd. | Structure en nid d'abeille |
CN103449840B (zh) * | 2013-08-28 | 2014-12-10 | 北京中安四海节能环保工程技术有限公司 | 一种蜂窝陶瓷载体及其制备方法 |
CN103804016A (zh) * | 2013-12-25 | 2014-05-21 | 大连润鸣材料技术有限公司 | 工程陶瓷 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4385129A (en) * | 1980-11-08 | 1983-05-24 | Nippon Soken, Inc. | Method for producing a cordierite body |
US4434117A (en) * | 1980-04-04 | 1984-02-28 | Nippon Soken, Inc. | Method for producing a cordierite body |
EP0278749A1 (fr) * | 1987-02-12 | 1988-08-17 | Ngk Insulators, Ltd. | Corps de cordiérite en structure en nid d'abeilles et méthode pour le produire |
EP0894777A1 (fr) * | 1997-07-28 | 1999-02-03 | Corning Incorporated | Procédé de fabrication de corps en cordiérite à partir de temps de frittage substantiellement réduit |
EP0894776A1 (fr) * | 1997-07-28 | 1999-02-03 | Corning Incorporated | Procédé de frittage accéléré pour des corps en cordiérite |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4772580A (en) * | 1985-12-27 | 1988-09-20 | Ngk Insulators, Ltd. | Catalyst carrier of cordierite honeycomb structure and method of producing the same |
JPH0669534B2 (ja) * | 1987-02-12 | 1994-09-07 | 日本碍子株式会社 | コージェライトハニカム構造体 |
JP2981034B2 (ja) * | 1991-09-30 | 1999-11-22 | 日本碍子株式会社 | セラミックハニカム構造体の焼成方法 |
-
1999
- 1999-02-09 CN CN 99802000 patent/CN1287546A/zh active Pending
- 1999-02-09 EP EP99906790A patent/EP1060149A4/fr not_active Withdrawn
- 1999-02-09 JP JP2000533391A patent/JP2002504476A/ja not_active Withdrawn
- 1999-02-09 WO PCT/US1999/002641 patent/WO1999043629A1/fr not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4434117A (en) * | 1980-04-04 | 1984-02-28 | Nippon Soken, Inc. | Method for producing a cordierite body |
US4385129A (en) * | 1980-11-08 | 1983-05-24 | Nippon Soken, Inc. | Method for producing a cordierite body |
EP0278749A1 (fr) * | 1987-02-12 | 1988-08-17 | Ngk Insulators, Ltd. | Corps de cordiérite en structure en nid d'abeilles et méthode pour le produire |
EP0894777A1 (fr) * | 1997-07-28 | 1999-02-03 | Corning Incorporated | Procédé de fabrication de corps en cordiérite à partir de temps de frittage substantiellement réduit |
EP0894776A1 (fr) * | 1997-07-28 | 1999-02-03 | Corning Incorporated | Procédé de frittage accéléré pour des corps en cordiérite |
Non-Patent Citations (1)
Title |
---|
See also references of WO9943629A1 * |
Also Published As
Publication number | Publication date |
---|---|
JP2002504476A (ja) | 2002-02-12 |
EP1060149A4 (fr) | 2002-07-17 |
CN1287546A (zh) | 2001-03-14 |
WO1999043629A1 (fr) | 1999-09-02 |
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17P | Request for examination filed |
Effective date: 20000922 |
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