CN111848208A - Wet spinning coextrusion preparation of straight-through hole zirconia ceramic with compact hole wall - Google Patents
Wet spinning coextrusion preparation of straight-through hole zirconia ceramic with compact hole wall Download PDFInfo
- Publication number
- CN111848208A CN111848208A CN202010559328.2A CN202010559328A CN111848208A CN 111848208 A CN111848208 A CN 111848208A CN 202010559328 A CN202010559328 A CN 202010559328A CN 111848208 A CN111848208 A CN 111848208A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- cell body
- interface layer
- hole
- precursor
- 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- Withdrawn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
Images
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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
-
- 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
-
- 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
-
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal thereof
-
- 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
-
- 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
- C04B38/0003—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof containing continuous channels, e.g. of the "dead-end" type or obtained by pushing bars in the green ceramic product
-
- 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
- C04B2235/60—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
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a method for preparing a straight-through hole zirconia ceramic with a compact hole wall by wet spinning coextrusion, which is characterized by comprising the following steps: 1) firstly, adding a curing agent and a plasticizer into an organic solvent, stirring and dissolving, then respectively adding ceramic powder of a cell body of a monolithic precursor and a cell body interface layer to form spinning slurry with two different components, pouring the spinning slurry into different injectors, spraying the spinning slurry into a gel tank through a co-extrusion spinning head under mechanical pressure, and carrying out solidification forming to obtain the monolithic precursor with the interface layer; 2) warm-pressing and forming; 3) vacuum degreasing; 4) hot pressing and sintering; 5) high-temperature oxidation to obtain the straight-through hole zirconia ceramics with compact hole walls. The microstructure of the straight-through hole zirconia ceramic obtained by the invention is accurately controlled, the hole wall is completely compact, the strength and the toughness are high, the hole wall thickness can reach 250 mu m, and the hole diameter can reach micron level.
Description
Technical Field
The invention provides a method for preparing a straight-through pore zirconia ceramic with a compact pore wall by wet spinning coextrusion, 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. Further reducing the aperture size of the through hole ceramic and improving the compactness of the hole wall 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 pore ceramic, and provides a method for preparing the through pore zirconia ceramic with compact pore wall by wet spinning coextrusion. The technical scheme is as follows:
a wet spinning coextrusion method for preparing a straight-through hole zirconia ceramic with compact hole walls is characterized by comprising the following steps:
1) preparing a fibrous monolith precursor with an interface layer by wet spinning coextrusion: firstly adding a curing agent and a plasticizer into an organic solvent, stirring and dissolving, then respectively adding ceramic powder of a monolithic precursor cell body and ceramic powder of a monolithic precursor cell body interface layer, uniformly stirring to form two spinning slurry with different components, then respectively pouring the spinning slurry into different injectors, spraying the spinning slurry into a gel tank filled with water through a co-extrusion spinning head under the mechanical pressure, wherein the water temperature of the gel tank is 0-10 ℃, soaking for 8-24 hours after solidification and forming, obtaining a fibromonolithic precursor with an interface layer, wherein the fibromonolithic precursor with the interface layer consists of a fibromonolithic precursor cell body and a cell body interface layer, the diameter of the fibromonolithic precursor cell body is 500-2000 mu m, the thickness of the cell body interface layer is 250-1000 mu m, wherein the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and the organic solvent is absolute ethyl alcohol;
2) 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 60-100 ℃ and under the pressure of 20-50 MPa to obtain a ceramic green body;
3) 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;
4) hot-pressing and sintering: after degreasing, hot-pressing and sintering in an argon atmosphere, wherein the sintering temperature is 1500-1600 ℃, the temperature is kept for 0.5-2 h, and the pressure is 20-60 MPa, so that the fiber monolithic ceramic is obtained;
5) high-temperature oxidation: oxidizing the fibrous monolith ceramic at 1000-1200 ℃, and removing cells by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 250-1000 mu m, and the thickness of the hole walls is 250-1000 mu m.
The wet spinning coextrusion is used for preparing the straight-through-hole zirconia ceramic with compact hole walls, and in the step 1), the ceramic powder for preparing the monolithic precursor cell body consists of carbon black powder or charcoal powder.
In the step 1), the ceramic powder for preparing the monolithic precursor cell body interface layer is prepared from zirconium oxide powder, yttrium oxide powder and magnesium oxide powder according to the mass percentage of 90-96%: 2-5%: 2-5% by weight.
In the step 1), based on the weight of ceramic powder for preparing the monolithic precursor cell body, 10-20% of a curing agent, 10-20% of a plasticizer and 100-200% of an organic solvent are weighed according to weight percentage.
In the step 1), based on the weight of ceramic powder for preparing a monolithic precursor cell interface layer, 10-20% of a curing agent, 10-20% of a plasticizer and 100-200% of an organic solvent are weighed according to weight percentage.
The working principle of the invention is as follows: provides a new process for preparing the straight-through pore zirconia ceramics with compact pore walls by a wet spinning coextrusion-hot pressing method. Firstly adding a curing agent and a plasticizer into an organic solvent, stirring and dissolving, then respectively adding ceramic powder of a monolithic precursor cell body and a monolithic precursor cell body interface layer, uniformly stirring to form spinning slurry with two different components, then extruding the two different spinning slurry from a co-extrusion spinning nozzle to be in a thin flow shape, and then curing and forming in a gel groove filled with water to obtain the monolithic precursor with the interface layer, wherein the structural schematic diagram is shown in figure 1, the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and the organic solvent is absolute ethyl alcohol; then arranging the fibrous monolithic precursors with the interface layers in parallel, carrying out warm-pressing molding, vacuum degreasing and hot-pressing sintering to prepare the fibrous monolithic ceramic, wherein the cell body is made of carbon black powder or charcoal powder material, and the cell body interface layer is made of zirconia-based material; and finally, oxidizing at the high temperature of 1000-1200 ℃, and removing the cell carbon black powder or the charcoal powder by oxidation to form the straight-through-hole zirconia ceramic with compact hole walls, wherein the structural schematic diagram is shown in figure 2, the hole walls are completely compact, and the hole diameter reaches the micron level.
Compared with the prior art, the invention has the following advantages:
1. the method comprises the following steps of forming a fibrous monolithic precursor with an interface layer by a wet spinning co-extrusion method, preparing the continuous, superfine, high-toughness and compact fibrous monolithic precursor with the interface layer, wherein the diameter of a cell body can reach 500 mu m, the thickness of the cell body interface layer can reach 250 mu m, the length of the cell body interface layer can reach more than 10 m, and the fibrous monolithic precursor 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, after the ceramic green body is degreased in vacuum, the polyvinyl butyral and the polyethylene glycol are cracked at high temperature into micromolecular carbon particles to be removed, no carbon residue exists, and the residual carbon can reduce the bending strength of the straight-through-hole zirconia ceramic;
3. the wet spinning co-extrusion method is used for forming the fiber monolithic precursor, so that the uneven thickness of the coating layer of the dipping method is changed, the process is simplified, and the accurate control of the microstructure of the straight-through-hole zirconia ceramic is achieved;
4. the prepared straight-through hole zirconia ceramic has completely compact hole walls, so that the straight-through hole zirconia ceramic has higher bending strength;
5. the through-hole zirconia ceramic is prepared through wet spinning, hot-pressing sintering and high-temperature oxidation, and the hole diameter reaches the micron level, which cannot be realized by the traditional pug extrusion molding;
6. The zirconium oxide phase transformation toughening mechanism is ZrO2When the ceramic is broken, the crack is expanded, the stress field at the tip of the crack induces t → m phase change, the volume of the phase change particles is expanded, and the volume expansion of the phase change particles generates compressive stress on the crack, so that the crack is hindered from expanding. Thus, only dense ZrO2The ceramic can be subjected to phase change toughening, and the wall of the through-hole zirconia ceramic prepared by the invention is compact, so that the ceramic has higher strength and better toughness.
Drawings
FIG. 1 is a schematic structural view of a fibrous monolith precursor having an interfacial layer according to the present invention;
FIG. 2 is a schematic structural diagram of a through-hole zirconia ceramic having dense pore walls according to the present invention.
In the figure: 1. a cell of a fibrous monolith precursor having an interfacial layer; 2. a cell interface layer of the fibrous monolith precursor having an interface layer; 3. the pore wall of the zirconia ceramic with the through pores; 4. a through hole of the through hole zirconia ceramic.
Detailed Description
Example 1
1. Preparing a fibromonolithic precursor cell body silk spraying liquid: firstly stirring and dissolving 10 g of polyvinyl butyral and 10 g of polyethylene glycol in 100 g of absolute ethyl alcohol, then adding ceramic powder of a fibromonolithic precursor cell body, wherein 100 g of the ceramic powder of the fibromonolithic precursor cell body consists of carbon black powder, and uniformly stirring to prepare a fibromonolithic precursor cell body silk spraying liquid;
2. Preparing a fiber monolith precursor cell body interface layer silk spraying liquid: firstly stirring and dissolving 10 g of polyvinyl butyral and 10 g of polyethylene glycol in 100 g of absolute ethyl alcohol, and then adding ceramic powder of a cell interface layer of a fiber monolithic precursor, wherein the ceramic powder of the cell interface layer of the fiber monolithic precursor is prepared from 90 g of zirconia powder, 5 g of yttria powder and 5 g of magnesia powder according to the mass percentage of 90%: 5%: 5 percent of the mixture is mixed and stirred evenly to prepare the fiber monolith precursor cell body interface layer silk spraying liquid;
3. wet spinning coextrusion to prepare a fibrous monolith precursor with an interfacial layer: respectively pouring the fibromonolithic precursor cell body silk spraying liquid and the fibromonolithic precursor cell body interface layer silk spraying liquid into different injectors, spraying the silk spraying slurry into a gel tank filled with water through a co-extrusion spinning nozzle under the mechanical pressure, wherein the water temperature of the gel tank is 0 ℃, and soaking for 8 hours after solidification forming to obtain the fibromonolithic precursor with the interface layer, wherein the fibromonolithic precursor with the interface layer consists of a fibromonolithic precursor cell body and a cell body interface layer, the diameter of the fibromonolithic precursor cell body is 500 mu m, and the thickness of the cell body interface layer is 250 mu m;
4. 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;
5. 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;
6. hot-pressing and sintering: after degreasing, hot-pressing and sintering under argon atmosphere, wherein the sintering temperature is 1500 ℃, the temperature is kept for 2h, and the pressure is 20MPa, so that the fiber monolithic ceramic is obtained;
7. high-temperature oxidation: oxidizing the fibromonolithic zirconia ceramic at 1000 ℃ for 5h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 250 mu m, and the hole wall thickness is 250 mu m.
Example 2
1. Preparing a fibromonolithic precursor cell body silk spraying liquid: firstly stirring and dissolving 20 g of polyvinyl butyral and 20 g of polyethylene glycol in 200 g of absolute ethyl alcohol, then adding ceramic powder of a fibromonolithic precursor cell body, wherein 100 g of the ceramic powder of the fibromonolithic precursor cell body consists of carbon black powder, and uniformly stirring to prepare a fibromonolithic precursor cell body silk spraying liquid;
2. preparing a fiber monolith precursor cell body interface layer silk spraying liquid: firstly stirring and dissolving 20 g of polyvinyl butyral and 20 g of polyethylene glycol in 200 g of absolute ethyl alcohol, and then adding ceramic powder of a cell interface layer of a fiber monolithic precursor, wherein the ceramic powder of the cell interface layer of the fiber monolithic precursor is composed of 96 g of zirconia powder, 2 g of yttria powder and 2 g of magnesia powder according to the mass percentage of 96%: 2%: 2 percent of the mixture is mixed and stirred evenly to prepare the fiber monolith precursor cell body interface layer silk spraying liquid;
3. Wet spinning coextrusion to prepare a fibrous monolith precursor with an interfacial layer: respectively pouring the fibromonolithic precursor cell body silk spraying liquid and the fibromonolithic precursor cell body interface layer silk spraying liquid into different injectors, spraying the silk spraying slurry into a gel tank filled with water through a co-extrusion spinning nozzle under mechanical pressure, wherein the water temperature of the gel tank is 10 ℃, and soaking for 24 hours after solidification forming to obtain the fibromonolithic precursor with an interface layer, wherein the fibromonolithic precursor with the interface layer consists of a fibromonolithic precursor cell body and a cell body interface layer, the diameter of the fibromonolithic precursor cell body is 2000 mu m, and the thickness of the cell body interface layer is 1000 mu m;
4. 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;
5. 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;
6. hot-pressing and sintering: after degreasing, hot-pressing and sintering under argon atmosphere, wherein the sintering temperature is 1600 ℃, the temperature is kept for 0.5h, and the pressure is 60MPa, so that the fiber monolithic ceramic is obtained;
7. High-temperature oxidation: oxidizing the fibromonolithic zirconia ceramic at 1200 ℃ for 1h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 1000 mu m, and the hole wall thickness is 1000 mu m.
Example 3
1. Preparing a fibromonolithic precursor cell body silk spraying liquid: firstly stirring and dissolving 15 g of polyvinyl butyral and 15 g of polyethylene glycol in 150 g of absolute ethanol, then adding ceramic powder of a monolithic precursor cell body, wherein 100 g of the ceramic powder of the monolithic precursor cell body consists of charcoal powder, and uniformly stirring to prepare a monolithic precursor cell body silk spraying liquid;
2. preparing a fiber monolith precursor cell body interface layer silk spraying liquid: firstly, stirring and dissolving 15 g of polyvinyl butyral and 15 g of polyethylene glycol in 150 g of absolute ethyl alcohol, and then adding ceramic powder of a cell interface layer of a fiber monolithic precursor, wherein the ceramic powder of the cell interface layer of the fiber monolithic precursor is prepared from 92 g of zirconia powder, 4 g of yttrium oxide powder and 4 g of magnesia powder according to the mass percentage of 92%: 4%: 4 percent of the mixture is mixed and stirred evenly to prepare the fiber monolith precursor cell body interface layer silk spraying liquid;
3. wet spinning coextrusion to prepare a fibrous monolith precursor with an interfacial layer: respectively pouring the fibromonolithic precursor cell body silk spraying liquid and the fibromonolithic precursor cell body interface layer silk spraying liquid into different injectors, spraying the silk spraying slurry into a gel tank filled with water through a co-extrusion spinning nozzle under the mechanical pressure, wherein the water temperature of the gel tank is 5 ℃, and soaking for 12 hours after solidification forming to obtain the fibromonolithic precursor with the interface layer, wherein the fibromonolithic precursor with the interface layer consists of a fibromonolithic precursor cell body and a cell body interface layer, the diameter of the fibromonolithic precursor cell body is 1000 mu m, and the thickness of the cell body interface layer is 500 mu m;
4. 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;
5. 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;
6. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at 1550 ℃, keeping the temperature for 1h and the pressure of 40MPa to obtain the fiber monolithic ceramic;
7. high-temperature oxidation: oxidizing the fibromonolithic zirconia ceramic at 1100 ℃ for 4h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 500 mu m, and the hole wall thickness is 500 mu m.
Example 4
1. Preparing a fibromonolithic precursor cell body silk spraying liquid: firstly stirring and dissolving 18 g of polyvinyl butyral and 18 g of polyethylene glycol in 180 g of absolute ethanol, then adding ceramic powder of a monolithic precursor cell body, wherein 100 g of the ceramic powder of the monolithic precursor cell body consists of charcoal powder, and uniformly stirring to prepare a monolithic precursor cell body silk spraying liquid;
2. Preparing a fiber monolith precursor cell body interface layer silk spraying liquid: firstly stirring and dissolving 18 g of polyvinyl butyral and 18 g of polyethylene glycol in 180 g of absolute ethyl alcohol, and then adding ceramic powder of a cell interface layer of a fiber monolithic precursor, wherein the ceramic powder of the cell interface layer of the fiber monolithic precursor is composed of 95 g of zirconia powder, 2 g of yttrium oxide powder and 3 g of magnesia powder according to the mass percentage of 95%: 2%: 3 percent of the mixture is mixed and stirred evenly to prepare the fiber monolith precursor cell body interface layer silk spraying liquid;
3. wet spinning coextrusion to prepare a fibrous monolith precursor with an interfacial layer: respectively pouring the fibromonolithic precursor cell body silk spraying liquid and the fibromonolithic precursor cell body interface layer silk spraying liquid into different injectors, spraying the silk spraying slurry into a gel tank filled with water through a co-extrusion spinning nozzle under mechanical pressure, wherein the water temperature of the gel tank is 2 ℃, and soaking for 10 hours after solidification forming to obtain the fibromonolithic precursor with the interface layer, wherein the fibromonolithic precursor with the interface layer consists of a fibromonolithic precursor cell body and a cell body interface layer, the diameter of the fibromonolithic precursor cell body is 800 mu m, and the thickness of the cell body interface layer is 400 mu m;
4. 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;
5. 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 1 ℃/min, and keeping the temperature for 0.5 h;
6. hot-pressing and sintering: after degreasing, hot-pressing and sintering under argon atmosphere, wherein the sintering temperature is 1560 ℃, the temperature is kept for 1h, and the pressure is 30MPa, so that the fiber monolithic ceramic is obtained;
7. high-temperature oxidation: oxidizing the fibromonolithic zirconia ceramic at 1050 ℃ for 3h, and removing cell bodies by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 400 mu m, and the hole wall thickness is 400 mu m.
Claims (5)
1. A wet spinning coextrusion method for preparing a straight-through hole zirconia ceramic with compact hole walls is characterized by comprising the following steps:
1) preparing a fibrous monolith precursor with an interface layer by wet spinning coextrusion: firstly adding a curing agent and a plasticizer into an organic solvent, stirring and dissolving, then respectively adding ceramic powder of a monolithic precursor cell body and ceramic powder of a monolithic precursor cell body interface layer, uniformly stirring to form two spinning slurry with different components, then respectively pouring the spinning slurry into different injectors, spraying the spinning slurry into a gel tank filled with water through a co-extrusion spinning head under the mechanical pressure, wherein the water temperature of the gel tank is 0-10 ℃, soaking for 8-24 hours after solidification and forming, obtaining a fibromonolithic precursor with an interface layer, wherein the fibromonolithic precursor with the interface layer consists of a fibromonolithic precursor cell body and a cell body interface layer, the diameter of the fibromonolithic precursor cell body is 500-2000 mu m, the thickness of the cell body interface layer is 250-1000 mu m, wherein the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and the organic solvent is absolute ethyl alcohol;
2) 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 60-100 ℃ and under the pressure of 20-50 MPa to obtain a ceramic green body;
3) 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;
4) hot-pressing and sintering: after degreasing, hot-pressing and sintering in an argon atmosphere, wherein the sintering temperature is 1500-1600 ℃, the temperature is kept for 0.5-2 h, and the pressure is 20-60 MPa, so that the fiber monolithic ceramic is obtained;
5) high-temperature oxidation: oxidizing the fibrous monolith ceramic at 1000-1200 ℃, and removing cells by oxidation to obtain the straight-through hole zirconia ceramic with compact hole walls, wherein the hole diameter is 250-1000 mu m, and the thickness of the hole walls is 250-1000 mu m.
2. The wet spun co-extrusion of claim 1 to produce a straight through pore zirconia ceramic having dense pore walls, wherein: in the step 1), the ceramic powder for preparing the fibrous monolith precursor cell body consists of carbon black powder or charcoal powder.
3. The wet spun co-extrusion of claim 1 to produce a straight through pore zirconia ceramic having dense pore walls, wherein: in the step 1), the ceramic powder for preparing the monolithic precursor cell body interface layer is prepared from 90-96% by mass of zirconium oxide powder, yttrium oxide powder and magnesium oxide powder: 2-5%: 2-5% by weight.
4. The wet spun co-extrusion of claim 1 to produce a straight through pore zirconia ceramic having dense pore walls, wherein: in the step 1), based on the weight of the ceramic powder for preparing the monolithic precursor cell body, 10-20% of a curing agent, 10-20% of a plasticizer and 100-200% of an organic solvent are weighed according to weight percentage.
5. The wet spun co-extrusion of claim 1 to produce a straight through pore zirconia ceramic having dense pore walls, wherein: in the step 1), based on the weight of the ceramic powder for preparing the monolithic precursor cell interface layer, 10-20% of a curing agent, 10-20% of a plasticizer and 100-200% of an organic solvent are weighed according to weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010559328.2A CN111848208A (en) | 2020-06-18 | 2020-06-18 | Wet spinning coextrusion preparation of straight-through hole zirconia ceramic with compact hole wall |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010559328.2A CN111848208A (en) | 2020-06-18 | 2020-06-18 | Wet spinning coextrusion preparation of straight-through hole zirconia ceramic with compact hole wall |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111848208A true CN111848208A (en) | 2020-10-30 |
Family
ID=72987242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010559328.2A Withdrawn CN111848208A (en) | 2020-06-18 | 2020-06-18 | Wet spinning coextrusion preparation of straight-through hole zirconia ceramic with compact hole wall |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111848208A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896553A (en) * | 2021-09-30 | 2022-01-07 | 中国人民解放军国防科技大学 | Fiber monolithic structure ultrahigh-temperature ceramic composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050020578A (en) * | 2003-08-18 | 2005-03-04 | 이병택 | A continuously porous ceramic body by fibrous monolithic process and manufacturing method thereof |
| CN101555138A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院金属研究所 | Silicon carbide foamed ceramic corrugated plate and preparation method thereof |
| CN108191453A (en) * | 2018-04-04 | 2018-06-22 | 刘成云 | A kind of porous silicon carbide ceramic and preparation method thereof |
| 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 |
| CN109293384A (en) * | 2018-10-31 | 2019-02-01 | 哈尔滨工业大学 | A method of preparing isotropic zirconium boride based ultra-high temperature monolithic structure ceramics in the face of high damage tolerance |
-
2020
- 2020-06-18 CN CN202010559328.2A patent/CN111848208A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050020578A (en) * | 2003-08-18 | 2005-03-04 | 이병택 | A continuously porous ceramic body by fibrous monolithic process and manufacturing method thereof |
| CN101555138A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院金属研究所 | Silicon carbide foamed ceramic corrugated plate and preparation method thereof |
| CN108191453A (en) * | 2018-04-04 | 2018-06-22 | 刘成云 | A kind of porous silicon carbide ceramic and preparation method thereof |
| 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 |
| CN109293384A (en) * | 2018-10-31 | 2019-02-01 | 哈尔滨工业大学 | A method of preparing isotropic zirconium boride based ultra-high temperature monolithic structure ceramics in the face of high damage tolerance |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896553A (en) * | 2021-09-30 | 2022-01-07 | 中国人民解放军国防科技大学 | Fiber monolithic structure ultrahigh-temperature ceramic composite material and preparation method thereof |
| CN113896553B (en) * | 2021-09-30 | 2022-11-11 | 中国人民解放军国防科技大学 | Fiber monolithic structure ultrahigh-temperature ceramic composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108794033B (en) | Self-toughening fiber monolithic structure ceramic and preparation method thereof | |
| TWI430975B (en) | Composition for ceramic extrusion-molded body and method for manufacturing a ceramic extrusion-molded body | |
| CN111825448B (en) | Method for preparing straight-through-hole zirconia ceramic with compact hole wall by wet spinning dipping method | |
| CN110922204A (en) | Preparation method of low-temperature sintered alumina ceramic membrane | |
| US8101117B2 (en) | Controlled gas pore formers in extruded ware | |
| CN108911779A (en) | Method for preparing porous silicon carbide ceramic tube at low temperature through extrusion molding | |
| CN111848158B (en) | Method for preparing straight-through-hole zirconia ceramic with compact hole wall by wet spinning coextrusion | |
| CN111848208A (en) | Wet spinning coextrusion preparation of straight-through hole zirconia ceramic with compact hole wall | |
| CN105727756B (en) | A kind of pair of gradient pore structured Sialon silicon carbide membrane tube and preparation method thereof | |
| CN113999046B (en) | Preparation method of low-temperature reaction sintered silicon carbide ceramic membrane | |
| US7914718B2 (en) | Gas pore former in cellular monoliths | |
| CN111848167A (en) | Preparation of exoskeleton structure fiber monolithic zirconium carbide ceramic by wet spinning coextrusion | |
| CN111875407A (en) | Wet spinning coextrusion preparation of straight-through hole alumina ceramic with compact hole wall | |
| CN111848138B (en) | Wet spinning-dipping process for preparing straight-through hole alumina ceramic with compact hole wall | |
| CN111892407B (en) | Wet spinning-dipping method for preparing double-interface fiber monolithic zirconium boride composite material | |
| CN102172960A (en) | Powder injection molding method for silicon carbide ceramic sand-blasting nozzle | |
| CN113270591B (en) | Preparation method of anode-supported SOFC electrolyte film | |
| CN111848175A (en) | Process for preparing weak interface fiber monolithic hafnium boride ceramic by wet spinning coextrusion method | |
| CN111892406B (en) | Preparation of weak interface fiber monolithic zirconium boride ultra-high temperature ceramic by wet spinning-dipping method | |
| Millán et al. | Gel‐Extrusion: A New Continuous Forming Technique | |
| CN111875406A (en) | Wet spinning coextrusion for preparing SiCwFibrous monolithic zirconium boride ceramic as interface | |
| Larbot | Ceramic processing techniques of support systems for membranes synthesis | |
| CN118005422B (en) | Direct-writing type 3D printing porous quartz ceramic pug and preparation method of porous quartz ceramic material | |
| CN115745635B (en) | Production method of combined ceramic wire drawing crucible | |
| Carter et al. | Shaping and forming |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201030 |