CN101429050B - Method for producing porous ceramic with oriented structure by employing freeze dehydration - Google Patents
Method for producing porous ceramic with oriented structure by employing freeze dehydration Download PDFInfo
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- CN101429050B CN101429050B CN2008102390162A CN200810239016A CN101429050B CN 101429050 B CN101429050 B CN 101429050B CN 2008102390162 A CN2008102390162 A CN 2008102390162A CN 200810239016 A CN200810239016 A CN 200810239016A CN 101429050 B CN101429050 B CN 101429050B
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Abstract
The invention discloses a method for preparing porous ceramics with a directive structure by a freeze drying method, which is a forming method for directly obtaining the porous ceramics by using congelation of ceramic slurry and decompression, drying and removal of impurities. Compared with other porous preparation technologies, the method is a method capable of preparing porous materials with high directing property, high porosity and complex shape, does not add a large quantity of organic pore forming materials, and is an environment-friendly technology. The main characteristic of the method is to control a porous structure by using the action of the medium solidifying process on ceramic particles. The porous ceramic materials are prepared by adding 0.5 to 5 grams of ammonium polyacrylate, 20 to 100 milliliters of deionized water and 0.5 to 5 milliliters of polyvinyl alcohol into 100 grams of alpha-alumina.
Description
Technical field
The present invention relates to a kind of method of making porous ceramic film material, more particularly say, be meant that a kind of employing freeze-drying method prepares the orienting stephanoporate stupalith.The orienting stephanoporate stupalith that makes has vesicular structure, and is parallel to the micropore that distributes on the directed duct of freezing temp gradient direction and the hole wall by macroscopic and constitutes.
Background technology
Improving constantly of the preceding fuel gas temperature of aero-turbine require the raising of blade cooling efficiency, and the key of this technology is the manufacturing of ceramic core.At present existing efficient air cooling blade ceramic core mainly is divided into silica-based and two kinds of alumina bases.Compare with silica-based ceramic core, alumina ceramic core metallurgical chemistry stability, creep-resistant property are good, can guarantee the dimensional precision and the qualification rate of the directional columnargrain and the single crystal hollow blade of inner-cavity structure complexity, and can reduce the manufacturing cost of blade.Yet the main component of the aluminum oxide core that uses is a corundum at present, and it reacts with the concentrated acid concentrated base under the condition of normal temperature and heating hardly, therefore is difficult to remove.
Perviousness and flourishing specific surface area with porous ceramics Yin Qigao of open-celled structure can be widely used in many-sides such as gas liquid filtration, purification separation, chemical industry catalytic carrier, sound absorption damping, senior lagging material, biological implantation material, extraordinary materials for wall and sensor materials.At present, porous material preparation technology has the foam impregnation method, adds pore-forming material method, extruding-out process, sol-gel technology etc., but these methods all have certain limitation, such as organism easily cause the suitable material of environmental pollution, technology limited, pore structure be difficult to control etc.
Summary of the invention
The objective of the invention is to propose a kind ofly to adopt freeze-drying preparation to have the technology of oriented structure porous ceramics, thereby be to utilize cryocoagulation ceramic size, drying under reduced pressure to get rid of the forming method that medium directly obtains porous ceramics, preparation technology compares with other porous, it is a kind of method that can prepare high directionality, high porosity and complicated shape porous material, do not add a large amount of organic pore-forming agents, be a kind of environment-friendly type technique, its maximum characteristics are to utilize the medium solidification process that the effect of ceramic particle is controlled its vesicular structure.
The present invention adopts the freeze-drying preparation to have the technology of oriented structure porous ceramics, be that scattered stable ceramic size is injected mould, be lower than under the liquid dispersion medium temperature of solidification condition, the liquid phase medium freezing and crystallizing, make slurry curing, the solid ceramic particle is extruded gathering in this process, form the poly-partially special construction of solid state medium powder, the body that freezes after the curing places and makes the medium that the freezes discharge that directly distils under the low pressure environment, obtain exsiccant, has along the porous ceramics base substrate of freezing temp gradient direction directional hole structure the porous ceramic film material that last sintering at high temperature obtains having certain physical strength.Can realize void content, pore Structure Control by factors such as control slurry solids content, chilling rate, powder dispersion staties to porous material.Air hole structure can be controlled; The organic additive of introducing is few, helps environmental protection; Dry, sintering shrinks little, can realize the dead size moulding.This porous ceramic film material is the ammonium polyacrylate that adds 0.5～5g in the Alpha-alumina of 100g, 20～100ml deionized water, the polyvinyl alcohol of 0.5～5ml.
Description of drawings
Fig. 1 is the stereoscan photograph that sample that the embodiment of the invention 1 makes is parallel to the freezing temp gradient direction.
Fig. 2 is the sample pore size distribution curve that the embodiment of the invention 1 makes.
Fig. 3 is the sample pore size distribution curve that the embodiment of the invention 3 makes.
Fig. 4 is the sample pore size distribution curve that the embodiment of the invention 4 makes.
Fig. 5 is the sample pore size distribution curve that the embodiment of the invention 5 makes.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention a kind ofly adopts freeze-drying preparation to have the technology of oriented structure Alpha-alumina porous ceramic film material, and starting material are Alpha-alumina (α-Al
2O
3), dispersion agent is ammonium polyacrylate (NH
4PAA), binding agent is polyvinyl alcohol (PVA) and deionized water.
Add starting material, dispersion agent, deionized water in ball grinder, ball milling was prepared slurry after 0.5～2 hour; In slurry, add binding agent and mix and regulate the pH value within 7～11.5, mix injection molding then, and to put into the refrigerant temperature be that-20 ℃～-100 ℃ freezing plants carry out after freezing 0.5～5 hour taking out, and places in the vacuum chamber and obtain biscuit after 5～15 hours; Biscuit is put into High Temperature Furnaces Heating Apparatus at 1300 ℃～1550 ℃, and sintering was cooled to room temperature with furnace temperature after 1～3 hour, made the porous ceramic film material with oriented structure.
The dispersion agent that adds 0.5～5g in the starting material of consumption: 100g, 20～100ml deionized water, the binding agent of 0.5～5ml.
The porous ceramic film material of the oriented structure that aforesaid method is made adopts Archimedes's drainage to test its void content, adopts the material mechanical performance tester to test its ultimate compression strength, adopts mercury injection apparatus to test its pore size distribution, adopts its microtexture of scanning electron microscopic observation.
The void content of the porous ceramic film material of the oriented structure that technology of the present invention makes is 41.9～75.7%.
The ultimate compression strength of the porous ceramic film material of the oriented structure that technology of the present invention makes is 0.3～160.9MPa.
Embodiment 1:
Adopt the freeze-drying preparation to have the α-Al of oriented structure
2O
3Porous ceramic film material.
Used starting material are Alpha-alumina (α-Al
2O
3), dispersion agent is ammonium polyacrylate (NH
4PAA), binding agent is polyvinyl alcohol (PVA).
α-the Al that in ball grinder, adds 100g
2O
3, 1g NH
4The deionized water of PAA, 30.5ml, ball milling was prepared slurry after 0.5 hour; Mix injection molding after in slurry, adding the PVA solution of 5ml and regulating pH to 8.5, and put into the refrigerant temperature, place and obtain biscuit in the vacuum chamber after 5 hours for-20 ℃ of freezing plants carry out taking out after freezing 0.5 hour; Biscuit is put into High Temperature Furnaces Heating Apparatus at 1300 ℃, and sintering was cooled to room temperature with furnace temperature after 1 hour, made the α-Al with oriented structure
2O
3Porous ceramic film material.
Adopt the test of Archimedes's drainage to have the α-Al of oriented structure
2O
3The void content of porous ceramic film material is 41.9%.
Adopt the test of material mechanical performance tester to have the α-Al of oriented structure
2O
3The ultimate compression strength of porous ceramic film material is 105.4MPa.
The α-Al that adopts scanning electron microscopic observation to make with oriented structure
2O
3The microstructure of porous ceramic film material, as shown in Figure 1.Among the figure, macroscopical duct is evenly distributed, and is parallel to the freezing temp gradient direction.
The α-Al that adopts the mercury injection apparatus test to make with oriented structure
2O
3The pore size distribution of porous ceramic film material, as shown in Figure 2.Among the figure, meso-position radius is positioned at 3 microns hole correspondence and macroscopical duct shown in Figure 1.
Embodiment 2:
Adopt the freeze-drying preparation to have the α-Al of oriented structure
2O
3Porous ceramic film material.
α-the Al that in ball grinder, adds 100g
2O
3, 0.5g NH
4The deionized water of PAA, 100ml, ball milling was prepared slurry after 0.5 hour; Mix injection molding after in slurry, adding the PVA solution of 5ml and regulating pH to 8.5, and put into the refrigerant temperature, place and obtain biscuit in the vacuum chamber after 5 hours for-20 ℃ of freezing plants carry out taking out after freezing 0.5 hour; Biscuit is put into High Temperature Furnaces Heating Apparatus at 1300 ℃, and sintering was cooled to room temperature with furnace temperature after 1 hour, made the α-Al with oriented structure
2O
3Porous ceramic film material.
Adopt the test of Archimedes's drainage to have the α-Al of oriented structure
2O
3The void content of porous ceramic film material is 75.7%.
Adopt the test of material mechanical performance tester to have the α-Al of oriented structure
2O
3The ultimate compression strength of porous ceramic film material is 0.3MPa.
Embodiment 3:
α-the Al that in ball grinder, adds 100g
2O
3, 5g NH
4The deionized water of PAA, 37.5ml, ball milling was prepared slurry after 0.5 hour; Mix injection molding after in slurry, adding the PVA solution of 5ml and regulating pH to 8.5, put into the refrigerant temperature, place and obtain biscuit in the vacuum chamber after 5 hours for-20 ℃ of freezing plants carry out taking out after freezing 0.5 hour; Biscuit is put into High Temperature Furnaces Heating Apparatus at 1550 ℃, and sintering was cooled to room temperature with furnace temperature after 1 hour, made the α-Al with oriented structure
2O
3Porous ceramic film material.
Adopt the test of Archimedes's drainage to have the α-Al of oriented structure
2O
3The void content of porous ceramic film material is 40.1%.
Adopt the test of material mechanical performance tester to have the α-Al of oriented structure
2O
3The ultimate compression strength of porous ceramic film material is 160.9MPa。
The α-Al that adopts the mercury injection apparatus test to make with oriented structure
2O
3The pore size distribution of porous ceramic film material, as shown in Figure 3.Among the figure, meso-position radius position, macroscopical duct is 4.3 microns, and the micropore meso-position radius is 1.1 microns.
Embodiment 5:
α-the Al that in ball grinder, adds 100g
2O
3, 1g NH
4The deionized water of PAA, 37.5ml, ball milling was prepared slurry after 0.5 hour; Mix injection molding after in slurry, adding the PVA solution of 5ml and regulating pH to 8.5, put into the refrigerant temperature, place and obtain biscuit in the vacuum chamber after 5 hours for-80 ℃ of freezing plants carry out taking out after freezing 0.5 hour; Biscuit is put into High Temperature Furnaces Heating Apparatus at 1300 ℃, and sintering was cooled to room temperature with furnace temperature after 1 hour, made the α-Al with oriented structure
2O
3Porous ceramic film material.
Adopt the test of Archimedes's drainage to have the α-Al of oriented structure
2O
3The void content of porous ceramic film material is 57.3%.
The α-Al that adopts the mercury injection apparatus test to make with oriented structure
2O
3The pore size distribution of porous ceramic film material, as shown in Figure 4.Among the figure, meso-position radius position, macroscopical duct is 3.2 microns, and the micropore meso-position radius is 1.1 microns.
Embodiment 6:
α-the Al that in ball grinder, adds 100g
2O
3, 1g NH
4The deionized water of PAA, 50ml, ball milling was prepared slurry after 0.5 hour; The PVA solution that adds 5ml in slurry mixes the back injection molding; After regulating slurry pH value to 10.0, put into the refrigerant temperature, place and obtain biscuit in the vacuum chamber after 5 hours for-20 ℃ of freezing plants carry out taking out after freezing 0.5 hour; Biscuit is put into High Temperature Furnaces Heating Apparatus at 1300 ℃, and sintering was cooled to room temperature with furnace temperature after 1 hour, made the α-Al with oriented structure
2O
3Porous ceramic film material.
Adopt the test of Archimedes's drainage to have the α-Al of oriented structure
2O
3The void content of porous ceramic film material is 60.1%.
Adopt the test of material mechanical performance tester to have the α-Al of oriented structure
2O
3The ultimate compression strength of porous ceramic film material is 35.4MPa.
The α-Al that adopts the mercury injection apparatus test to make with oriented structure
2O
3The pore size distribution of porous ceramic film material, as shown in Figure 5.Among the figure, meso-position radius position, macroscopical duct is 10.1, and the micropore meso-position radius is 1.1.
Claims (3)
1. one kind is adopted freeze-drying preparation to have the method for oriented structure porous ceramics, it is characterized in that: this porous ceramic film material is the ammonium polyacrylate that adds 0.5～5g in the Alpha-alumina of 100g, 20～100ml deionized water, the polyvinyl alcohol of 0.5～5ml;
Add Alpha-alumina, ammonium polyacrylate, deionized water in ball grinder, ball milling was prepared slurry after 0.5～2 hour; The interpolation polyvinyl alcohol mixes evenly and regulates the pH value within 7～11.5 in slurry, mix injection molding then, and to put into the refrigerant temperature be that-20 ℃～-100 ℃ freezing plants carry out after freezing 0.5～5 hour taking out, and places in the vacuum chamber and obtain biscuit after 5～15 hours; Biscuit is put into High Temperature Furnaces Heating Apparatus at 1300 ℃～1550 ℃, and sintering was cooled to room temperature with furnace temperature after 1～3 hour, made the porous ceramic film material with oriented structure.
2. employing freeze-drying preparation according to claim 1 has the method for oriented structure porous ceramics, and it is characterized in that: the void content of the porous ceramic film material that makes is 41.9～75.7%.
3. employing freeze-drying preparation according to claim 1 has the method for oriented structure porous ceramics, and it is characterized in that: the ultimate compression strength of the porous ceramic film material that makes is 0.3～160.9MPa.
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| CN102285815B (en) * | 2011-06-07 | 2013-03-13 | 西安理工大学 | Method for preparing double-pore type porous ceramic |
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| CN116173947A (en) * | 2021-11-29 | 2023-05-30 | 中国华能集团清洁能源技术研究院有限公司 | Hydrogenation catalyst and preparation method and application thereof |
| CN114436674B (en) * | 2022-02-11 | 2023-04-11 | 洛阳理工学院 | Preparation method of network-like silicon carbide fiber |
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