CN111848138A - Wet spinning-dipping process for preparing straight-through hole alumina ceramic with compact hole wall - Google Patents

Wet spinning-dipping process for preparing straight-through hole alumina ceramic with compact hole wall Download PDF

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CN111848138A
CN111848138A CN202010558594.3A CN202010558594A CN111848138A CN 111848138 A CN111848138 A CN 111848138A CN 202010558594 A CN202010558594 A CN 202010558594A CN 111848138 A CN111848138 A CN 111848138A
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hole
alumina
interface layer
cell body
powder
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CN111848138B (en
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魏春城
王鹏
潘光慎
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Rizhao Dingyuan New Material Co ltd
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Abstract

The invention provides a wet spinning-dipping method for preparing straight-through hole alumina ceramics with compact hole walls, which is characterized by comprising the following steps: 1) preparing a monolithic precursor cell body by adopting a wet spinning method, stirring and dissolving a curing agent and a plasticizer in an organic solvent, adding carbon black ceramic powder to prepare a spinning solution, spraying the spinning solution into a gel tank through a spinning nozzle, and performing solidification forming to obtain the monolithic precursor cell body; 2) coating an interface layer by an immersion method, immersing the fibrous monolith precursor cell body into alumina slurry, and controlling the thickness of the interface layer by dipping and pulling times to obtain the fibrous monolith precursor with the interface layer; 3) warm-pressing and forming; 4) vacuum degreasing; 5) hot pressing and sintering; 6) high-temperature oxidation to obtain the straight-through hole alumina ceramic with compact hole walls. The through-hole alumina ceramic obtained by the invention has the advantages that the hole wall is completely compact, the strength is high, the hole wall thickness can reach 50 mu m, and the hole diameter can reach micron level.

Description

Wet spinning-dipping process for preparing straight-through hole alumina ceramic with compact hole wall
Technical Field
The invention provides a wet spinning-dipping method for preparing straight-through hole alumina ceramics with compact hole walls, belonging to the technical field of preparation of porous ceramics.
Background
The porous ceramic has the characteristics of small volume density, high porosity, large specific surface area, selective permeability to liquid and gas media, energy absorption or damping characteristic and the like, particularly the straight-through porous ceramic has a parallel through cellular pore channel structure in the straight-through porous ceramic, is favorable for the entrance of reactants and the discharge of products, has a large geometric surface, and has uniform flow distribution of fluid in the straight-through porous ceramic, so the straight-through porous ceramic is widely applied to various aspects such as gas-liquid filtration, purification and separation and the like. The traditional method for preparing the straight-through porous ceramic is mud extrusion molding, namely dry spinning molding, wherein a green body is aged and pugged in vacuum to enable the green body to have certain plasticity, and the green body is continuously molded through a neck mold with a certain shape under the extrusion action of a screw or a plunger of an extruder. However, the prepared through-hole ceramic has the following defects: first, the aperture is big, and the aperture is generally at the millimeter level, because the pug has plasticity, and the contractility is big, and the aperture undersize is easy to be blockked up. Secondly, the thickness of the hole wall is thinner, the extrusion pressure is higher, and the straight-through hole ceramic with the hole wall smaller than 1mm is difficult to form; thirdly, the hole wall is not compact, most of the raw materials for extrusion molding belong to barren materials, and the raw materials have no plasticity. It must be plasticized prior to extrusion, usually by the addition of plasticizers or binders. Organic plasticizers such as dextrin, industrial syrup, carboxymethyl cellulose, polyvinyl acetate and polyvinyl alcohol are commonly used in industrial production. The addition of the organic plasticizer forms holes after sintering, reduces the compactness of the hole wall, and further ensures that the bending strength of the through hole ceramic prepared by extrusion molding is lower. Therefore, the pore size of the through hole ceramic is further reduced, and the compactness of the pore wall is improved, so that the method has important theoretical significance and practical value for popularization and application of the through hole ceramic.
Disclosure of Invention
The invention aims to solve the problems of large aperture and non-compact pore wall of the existing through-hole ceramic, and provides a wet spinning-dipping method for preparing through-hole alumina ceramic with compact pore walls. The technical scheme is as follows:
a wet spinning-dipping method for preparing straight-through hole alumina ceramics with compact hole walls is characterized by comprising the following steps:
1) preparing a precursor cell body of the fiber monolith by adopting a wet spinning method: firstly stirring and dissolving a curing agent and a plasticizer in an organic solvent, then adding carbon black ceramic powder, strongly stirring for 12-48 h to prepare a spinning solution, then moving the spinning solution to a stainless steel storage tank, vacuum degassing for 1-5 h, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.2-0.5 MPa, wherein the water temperature of the gel tank is 0-10 ℃, and soaking for 8-24 h after solidification forming to obtain a monolithic precursor cell body, wherein the diameter of the monolithic precursor cell body is 200-2000 mu m, when weighing, firstly weighing the carbon black ceramic powder, and then weighing 10-20% of the curing agent, 10-20% of the plasticizer and 100-200% of the organic solvent according to the weight percentage by taking the carbon black ceramic powder as a basis;
2) coating an interface layer by a dipping method: adding a binder into deionized water, uniformly stirring, adding alumina ceramic powder, stirring for 4-12 h to form alumina slurry, coating by adopting a dipping method, dipping a fibrous monolithic precursor cell body into the alumina slurry, controlling the thickness of an interface layer by dipping and pulling times, wherein the thickness of the interface layer is 50-200 mu m, so as to obtain the fibrous monolithic precursor with the interface layer, the fibrous monolithic precursor with the interface layer consists of the fibrous monolithic precursor cell body and the interface layer, wherein the binder is carboxymethyl cellulose, and the alumina ceramic powder consists of alumina powder, yttrium oxide powder and magnesium oxide powder according to the mass percentage of 90-96%: 2-5%: 2-5% by weight;
3) Warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor at the temperature of 60-200 ℃ and under the pressure of 20-50 MPa to obtain a ceramic green body;
4) vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, performing vacuum degreasing, wherein the heating rate is 0.25-1 ℃/min, the temperature is increased to 600-700 ℃, and the temperature is kept for 0.5-1 h;
5) hot-pressing and sintering: after degreasing, hot-pressing and sintering in an argon atmosphere, wherein the sintering temperature is 1700-1800 ℃, the temperature is kept for 0.5-2 h, and the pressure is 20-60 MPa, so that the fiber monolithic ceramic is obtained;
6) high-temperature oxidation: oxidizing the fiber monolithic ceramics at 1200-1500 ℃ for 1-5 h, and removing cells by oxidation to obtain the straight-through hole alumina ceramics with compact hole walls, wherein the hole diameter is 100-1000 mu m, and the hole wall thickness is 50-200 mu m.
The wet spinning-dipping method is used for preparing the straight-through hole alumina ceramic with compact hole walls, in the step 1), the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and the organic solvent is absolute ethyl alcohol.
The wet spinning-dipping method is used for preparing the straight-through hole alumina ceramic with compact hole walls, and in the step 1), the carbon black ceramic powder consists of carbon black powder or charcoal powder.
In the step 2), the preparation method of the alumina slurry comprises the steps of weighing alumina ceramic powder, and then weighing 2-5% of carboxymethyl cellulose and 500-2000% of deionized water by weight percentage based on the weight of the alumina ceramic powder.
The working principle of the invention is as follows: provides a new process for preparing the straight-through hole alumina ceramic with compact hole walls by a wet spinning-hot pressing method. Firstly, stirring and dissolving a curing agent and a plasticizer in an organic solvent, adding carbon black ceramic powder to form a spinning solution, extruding the spinning solution from fine holes of a spinning nozzle to be in a fine flow shape, and then curing and forming in a solidification solution to obtain a monolithic precursor cell body, wherein the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and the organic solvent is absolute ethyl alcohol; coating the alumina slurry by adopting an immersion method to obtain a fiber monolith precursor with an interface layer; parallel arrangement, warm-pressing molding, vacuum degreasing, hot-pressing sintering, and preparing the fiber monolithic ceramics, wherein the cell body is carbon black powder or charcoal powder material, and the interface layer is Al2O3A base material; and finally, oxidizing at 1200-1500 ℃ to remove the cell carbon black powder or charcoal powder by oxidation, and finally forming the straight-through hole alumina ceramic with compact hole walls, wherein the structural schematic diagram is shown in figure 1.
Compared with the prior art, the invention has the following advantages:
1. forming a fibrous monolithic precursor cell body by a wet spinning method, and preparing the continuous, superfine, high-toughness, compact and cylindrical fibrous monolithic precursor cell body, wherein the diameter can reach 200 mu m, the length can reach more than 10 m, and the fibrous monolithic precursor cell body can not be broken when bent by 180 degrees and is convenient to arrange;
2. the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and after the ceramic green body is degreased in vacuum, the polyvinyl butyral and the polyethylene glycol are pyrolyzed into micromolecular carbon particles to be removed without carbon residue, so that the straight-through hole alumina ceramic has higher strength;
3. dipping and coating an interface layer on the fibromonolith precursor cell body in alumina slurry taking deionized water as a solvent, wherein the fibromonolith precursor cell body is insoluble and uniformly coated, and the hole wall obtained after hot-pressing sintering is ultrathin and can reach 50 mu m in thickness;
4. the prepared straight-through hole alumina ceramic has completely compact hole walls, so that the straight-through hole alumina ceramic has higher bending strength;
5. the straight-through hole alumina ceramic is prepared through wet spinning, hot-pressing sintering and high-temperature oxidation, and the aperture can reach micron order, which can not be realized by traditional pug extrusion molding.
Drawings
FIG. 1 is a schematic structural view of a through-hole alumina ceramic having dense pore walls according to the present invention;
FIG. 2 is a photograph of a precursor cell of fibrous monolith obtained in example 1 of the present invention.
In the figure: 1. the pore wall of the straight-through pore alumina ceramic; 2. straight-through holes of the straight-through hole alumina ceramic.
Detailed Description
Example 1
1. Preparing a precursor cell body of the fiber monolith by adopting a wet spinning method: firstly stirring and dissolving 10 g of polyvinyl butyral and 10 g of polyethylene glycol in 100 g of absolute ethyl alcohol, then adding carbon black ceramic powder, wherein the carbon black ceramic powder consists of 100 g of carbon black powder, strongly stirring for 12h to prepare spinning solution, then transferring the spinning solution into a stainless steel storage tank, degassing for 1h in vacuum, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.2MPa, wherein the water temperature of the gel tank is 0 ℃, and soaking for 8h after solidification forming to obtain a monolithic precursor cell body, wherein the diameter of the monolithic precursor cell body is 200 mu m;
2. coating an interface layer by a dipping method: firstly adding 2 g of carboxymethyl cellulose into 500 g of deionized water, uniformly stirring, then adding alumina ceramic powder, stirring for 4h to form alumina slurry, coating by adopting a dipping method, dipping a monolithic fiber precursor cell body into the alumina slurry, controlling the thickness of an interface layer by dipping and pulling times, wherein the thickness of the interface layer is 50 mu m, so as to obtain a monolithic fiber precursor with the interface layer, wherein the alumina ceramic powder is prepared from 90 g of alumina powder, 5 g of yttrium oxide powder and 5 g of magnesium oxide powder according to the mass percent of 90%: 5%: 5 percent of the raw materials are mixed;
3. Warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and carrying out warm pressing at 60 ℃ and 20MPa to compact the fiber monolithic precursor to obtain a ceramic green body;
4. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 600 ℃ at the heating speed of 0.25 ℃/min, and keeping the temperature for 0.5 h;
5. hot-pressing and sintering: after degreasing, hot-pressing and sintering under argon atmosphere, wherein the sintering temperature is 1700 ℃, the temperature is kept for 0.5h, and the pressure is 20MPa, so that the fiber monolithic ceramic is obtained;
6. high-temperature oxidation: oxidizing the fibrous monolith ceramic at 1200 ℃ for 5h, and removing cells by oxidation to obtain the straight-through hole alumina ceramic with compact hole walls, wherein the hole diameter is 100 mu m, and the hole wall thickness is 50 mu m.
Example 2
1. Preparing a precursor cell body of the fiber monolith by adopting a wet spinning method: stirring and dissolving 20 g of polyvinyl butyral and 20 g of polyethylene glycol in 200 g of absolute ethyl alcohol, adding carbon black ceramic powder, wherein the carbon black ceramic powder consists of 100 g of carbon black powder, strongly stirring for 48h to prepare spinning solution, then transferring the spinning solution to a stainless steel storage tank, degassing for 5h in vacuum, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.5MPa, wherein the water temperature of the gel tank is 10 ℃, and soaking for 24h after solidification and forming to obtain a monolithic precursor cell body, wherein the diameter of the monolithic precursor cell body is 2000 mu m;
2. Coating an interface layer by a dipping method: firstly adding 5 g of carboxymethyl cellulose into 1000 g of deionized water, uniformly stirring, then adding alumina ceramic powder, stirring for 12h to form alumina slurry, coating by adopting a dipping method, dipping a monolithic precursor cell body into the alumina slurry, controlling the thickness of an interface layer by dipping and pulling times, wherein the thickness of the interface layer is 200 mu m, so as to obtain the monolithic precursor with the interface layer, wherein the alumina ceramic powder consists of 96 g of alumina powder, 2 g of yttrium oxide powder and 2 g of magnesium oxide powder according to the mass percent of 96%: 2%: 2 percent of the raw materials are mixed;
3. warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and carrying out warm pressing at 100 ℃ and 50MPa to compact the fiber monolithic precursor to obtain a ceramic green body;
4. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 700 ℃ at the heating speed of 1 ℃/min, and keeping the temperature for 1 h;
5. hot-pressing and sintering: after degreasing, hot-pressing and sintering under the argon atmosphere, wherein the sintering temperature is 1800 ℃, the temperature is kept for 2h, and the pressure is 60MPa, so that the fiber monolithic ceramic is obtained;
6. high-temperature oxidation: oxidizing the fiber monolithic ceramics at 1500 ℃ for 1h, and removing cells by oxidation to obtain the straight-through hole alumina ceramics with compact hole walls, wherein the hole diameter is 1000 mu m, and the hole wall thickness is 200 mu m.
Example 3
1. Preparing a precursor cell body of the fiber monolith by adopting a wet spinning method: firstly stirring and dissolving 15 g of polyvinyl butyral and 15 g of polyethylene glycol in 150 g of absolute ethyl alcohol, then adding carbon black ceramic powder, wherein the carbon black ceramic powder consists of 100 g of charcoal powder, strongly stirring for 24h to prepare spinning solution, then transferring the spinning solution into a stainless steel storage tank, degassing for 2h in vacuum, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.4MPa, wherein the water temperature of the gel tank is 5 ℃, and soaking for 12h after solidification forming to obtain a monolithic precursor cell body, wherein the diameter of the monolithic precursor cell body is 1000 mu m;
2. coating an interface layer by a dipping method: firstly adding 4 g of carboxymethyl cellulose into 800 g of deionized water, uniformly stirring, then adding alumina ceramic powder, stirring for 8h to form alumina slurry, coating by adopting a dipping method, dipping a monolithic fiber precursor cell body into the alumina slurry, controlling the thickness of an interface layer by dipping and pulling times, wherein the thickness of the interface layer is 100 mu m, obtaining a monolithic fiber precursor with the interface layer, and the alumina ceramic powder is prepared from 92 g of alumina powder, 4 g of yttrium oxide powder and 4 g of magnesium oxide powder according to the mass percentage of 92%: 4%: 4 percent of the components are mixed;
3. Warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and carrying out warm pressing at 80 ℃ and 30MPa to compact the fiber monolithic precursor to obtain a ceramic green body;
4. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, performing vacuum degreasing, wherein the heating rate is 0.5 ℃/min, the temperature is increased to 650 ℃, and the temperature is kept for 0.75 h;
5. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at 1750 ℃ for 1h under the pressure of 40MPa to obtain fiber monolithic ceramics;
6. high-temperature oxidation: oxidizing the fiber monolithic ceramics at 1300 ℃ for 4h, and removing cells by oxidation to obtain the straight-through hole alumina ceramics with compact hole walls, wherein the hole diameter is 500 mu m, and the hole wall thickness is 100 mu m.
Example 4
1. Preparing a precursor cell body of the fiber monolith by adopting a wet spinning method: firstly stirring and dissolving 18 g of polyvinyl butyral and 18 g of polyethylene glycol in 180 g of absolute ethyl alcohol, then adding carbon black ceramic powder, wherein the carbon black ceramic powder consists of 100 g of charcoal powder, strongly stirring for 30h to prepare spinning solution, then transferring the spinning solution to a stainless steel storage tank, degassing for 4h in vacuum, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.3MPa, wherein the water temperature of the gel tank is 5 ℃, and soaking for 20h after solidification forming to obtain a monolithic precursor cell body, wherein the diameter of the monolithic precursor cell body is 700 mu m;
2. Coating an interface layer by a dipping method: firstly adding 3 g of carboxymethyl cellulose into 700 g of deionized water, uniformly stirring, then adding alumina ceramic powder, stirring for 6h to form alumina slurry, coating by adopting a dipping method, dipping a monolithic precursor cell body into the alumina slurry, controlling the thickness of an interface layer by dipping and pulling times, wherein the thickness of the interface layer is 70 mu m, so as to obtain the monolithic precursor with the interface layer, and the alumina ceramic powder consists of 95 g of alumina powder, 2 g of yttrium oxide powder and 3 g of magnesium oxide powder according to the mass percentage of 95%: 2%: 3 percent of the raw materials are mixed;
3. warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and carrying out warm pressing at 70 ℃ and 40MPa to compact the fiber monolithic precursor to obtain a ceramic green body;
4. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 650 ℃ at the heating speed of 0.5 ℃/min, and keeping the temperature for 0.5 h;
5. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere, wherein the sintering temperature is 1780 ℃, the temperature is kept for 1h, and the pressure is 40MPa, so that the fiber monolithic ceramic is obtained;
6. high-temperature oxidation: oxidizing the fiber monolithic ceramic at 1400 ℃ for 3h, and removing cells by oxidation to obtain the straight-through hole alumina ceramic with compact hole walls, wherein the hole diameter is 350 mu m, and the hole wall thickness is 70 mu m.

Claims (4)

1. A wet spinning-dipping method for preparing straight-through hole alumina ceramics with compact hole walls is characterized by comprising the following steps:
1) preparing a precursor cell body of the fiber monolith by adopting a wet spinning method: firstly stirring and dissolving a curing agent and a plasticizer in an organic solvent, then adding carbon black ceramic powder, strongly stirring for 12-48 h to prepare a spinning solution, then moving the spinning solution to a stainless steel storage tank, vacuum degassing for 1-5 h, spraying the spinning solution into a gel tank filled with water through a spinning nozzle under the nitrogen pressure of 0.2-0.5 MPa, wherein the water temperature of the gel tank is 0-10 ℃, and soaking for 8-24 h after solidification forming to obtain a monolithic precursor cell body, wherein the diameter of the monolithic precursor cell body is 200-2000 mu m, when weighing, firstly weighing the carbon black ceramic powder, and then weighing 10-20% of the curing agent, 10-20% of the plasticizer and 100-200% of the organic solvent according to the weight percentage by taking the carbon black ceramic powder as a basis;
2) coating an interface layer by a dipping method: adding a binder into deionized water, uniformly stirring, adding alumina ceramic powder, stirring for 4-12 h to form alumina slurry, coating by adopting a dipping method, dipping a fibrous monolithic precursor cell body into the alumina slurry, controlling the thickness of an interface layer by dipping and pulling times, wherein the thickness of the interface layer is 50-200 mu m, so as to obtain the fibrous monolithic precursor with the interface layer, the fibrous monolithic precursor with the interface layer consists of the fibrous monolithic precursor cell body and the interface layer, wherein the binder is carboxymethyl cellulose, and the alumina ceramic powder consists of alumina powder, yttrium oxide powder and magnesium oxide powder according to the mass percentage of 90-96%: 2-5%: 2-5% by weight;
3) Warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor at the temperature of 60-200 ℃ and under the pressure of 20-50 MPa to obtain a ceramic green body;
4) vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, performing vacuum degreasing, wherein the heating rate is 0.25-1 ℃/min, the temperature is increased to 600-700 ℃, and the temperature is kept for 0.5-1 h;
5) hot-pressing and sintering: after degreasing, hot-pressing and sintering in an argon atmosphere, wherein the sintering temperature is 1700-1800 ℃, the temperature is kept for 0.5-2 h, and the pressure is 20-60 MPa, so that the fiber monolithic ceramic is obtained;
6) high-temperature oxidation: oxidizing the fiber monolithic ceramics at 1200-1500 ℃ for 1-5 h, and removing cells by oxidation to obtain the straight-through hole alumina ceramics with compact hole walls, wherein the hole diameter is 100-1000 mu m, and the hole wall thickness is 50-200 mu m.
2. The wet spin-dip process of claim 1 for preparing a through-hole alumina ceramic with dense pore walls, wherein: in the step 1), the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and the organic solvent is absolute ethyl alcohol.
3. The wet spin-dip process of claim 1 for preparing a through-hole alumina ceramic with dense pore walls, wherein: in the step 1), the carbon black ceramic powder consists of carbon black powder or charcoal powder.
4. The wet spin-dip process of claim 1 for preparing a through-hole alumina ceramic with dense pore walls, wherein: in the step 2), the preparation method of the alumina slurry comprises the steps of weighing alumina ceramic powder, and then weighing 2-5% of carboxymethyl cellulose and 500-2000% of deionized water according to the weight percentage based on the weight of the alumina ceramic powder.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11116352A (en) * 1997-10-15 1999-04-27 Asahi Glass Co Ltd Production of porous ceramic
CN102171162A (en) * 2008-09-30 2011-08-31 倍耐力&C.Eco技术股份公司 Honeycomb structural body for exhaust gas purification
CN103910520A (en) * 2013-09-27 2014-07-09 郑州大学 Preparation method for aluminium oxide porous ceramic
CN108794033A (en) * 2018-06-28 2018-11-13 中国科学院兰州化学物理研究所 A kind of self toughening fibrous monolithic ceramic structural ceramics and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11116352A (en) * 1997-10-15 1999-04-27 Asahi Glass Co Ltd Production of porous ceramic
CN102171162A (en) * 2008-09-30 2011-08-31 倍耐力&C.Eco技术股份公司 Honeycomb structural body for exhaust gas purification
CN103910520A (en) * 2013-09-27 2014-07-09 郑州大学 Preparation method for aluminium oxide porous ceramic
CN108794033A (en) * 2018-06-28 2018-11-13 中国科学院兰州化学物理研究所 A kind of self toughening fibrous monolithic ceramic structural ceramics and preparation method thereof

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