CN111807852B - Method for preparing high-porosity porous ceramic material - Google Patents
Method for preparing high-porosity porous ceramic material Download PDFInfo
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- CN111807852B CN111807852B CN202010686548.1A CN202010686548A CN111807852B CN 111807852 B CN111807852 B CN 111807852B CN 202010686548 A CN202010686548 A CN 202010686548A CN 111807852 B CN111807852 B CN 111807852B
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Abstract
The invention relates to a high-porosity porous ceramic material which is characterized by being prepared by sintering the following raw materials in parts by weight, 44.4-76.5 parts of water-based solution, 10-30 parts of ceramic powder, 0.1-1 part of dispersing agent, 1-8 parts of pore-forming agent, 1-6 parts of ceramic fiber and 1-5 parts of initiator. The invention is based on a water-based gel injection molding method, and adds pore-forming agent and ceramic fiber into a water-based solution, wherein the ceramic fiber forms a supporting framework, so that the shrinkage and cracking of raw materials during sintering are reduced, and the pore-forming agent forms a mesoporous-macroporous composite structure, thereby obtaining the high-porosity porous ceramic material with the mesoporous-macroporous composite structure.
Description
Technical Field
The invention relates to a method for preparing a porous ceramic material with high porosity, which can obtain the porous ceramic material with the porosity of more than 70 percent and belongs to the technical field of ceramic material preparation.
Background
The porous ceramic material has the advantages of good mechanical property, small thermal conductivity, high temperature resistance, corrosion resistance and the like, and is an ideal material for heat insulation. In some special use scenarios, for example, in the aerospace field, due to a harsh environment, a porous ceramic material with a better heat insulation effect is required, that is, the porosity of the porous ceramic material is required to be higher, and the porosity of the porous ceramic material is required to reach more than 70%.
Currently, among various methods for preparing porous ceramic materials, the gel injection molding method is the best method for preparing porous ceramic materials with porosity of more than 50%. Among them, the gel injection molding method can be classified into a non-aqueous system and an aqueous system depending on the solvent. If the solvent is an organic solvent (e.g., t-butanol as a solvent), the method is a non-aqueous gel casting method; if the solvent is water, the process is referred to as water-based gel-casting. Among them, the non-aqueous gel injection molding method is gradually eliminated due to the problems of high cost of the solvent, environmental pollution of the solvent and the like.
When the water-based gel injection molding method is adopted to prepare the high-porosity porous ceramic material, the following problems can be caused:
1. because a large amount of solvent needs to be removed in the preparation of the porous ceramic material with high porosity, the solid content is low, and green body shrinkage and cracking can occur when a wet green body of the porous ceramic material is dried.
2. As the porous ceramic material with high porosity is prepared, the blank of the porous ceramic material excessively shrinks and cracks during sintering, and the porosity cannot be effectively maintained.
Therefore, it is difficult to obtain a porous ceramic material with a porosity of more than 70% by using a water-based gel injection molding method, and a method for solving the problem that a porous ceramic material with a porosity of more than 70% is difficult to obtain by using a water-based gel injection molding method is urgently needed.
Disclosure of Invention
According to one aspect of the invention, the high-porosity porous ceramic material is prepared by sintering the following raw materials in parts by weight, 44.4-76.5 parts of water-based solution, 10-30 parts of ceramic powder, 0.1-1 part of dispersing agent, 1-8 parts of pore-forming agent, 1-6 parts of ceramic fiber and 1-5 parts of initiator.
Further, the water-based solution comprises water, an organic monomer and a cross-linking agent, wherein the mixing ratio of the water, the organic monomer and the cross-linking agent is as follows in parts by weight: 40 to 60 portions of water, 4 to 15 portions of organic monomer and 0.4 to 1.5 portions of cross-linking agent.
Furthermore, the porosity of the porous ceramic material prepared by sintering is more than 70 percent, and the volume density is less than 1.4g/cm -3 The compressive strength is more than 5MPa; testing the thermal conductivity of the material by a flash method, wherein the thermal conductivity of the porous ceramic material is less than 0.1W/m.k; the porous ceramic material has a mesoporous-macroporous composite structure, and the size of the porous ceramic material is larger than 80 x 80mm or the diameter is larger than 80mm.
Compared with the prior art, the method has the advantages and beneficial effects that the method is based on a water-based gel injection molding method, the pore-forming agent and the ceramic fiber are added into the water-based solution, wherein the ceramic fiber forms a supporting framework, the shrinkage and cracking of the raw materials during sintering are reduced, the pore-forming agent forms a mesoporous-macroporous composite structure, and the high-porosity porous ceramic material with the mesoporous-macroporous composite structure is obtained.
Further, the pore-forming agent is PMMA microspheres, and the particle size D50 of the microspheres is 10-50 μm.
Further, the initiator includes one or more of ammonium sulfate, sodium persulfate, and potassium persulfate.
Further, the ceramic fiber is alumina fiber or boron nitride fiber, the diameter of the fiber is 0.5-5 μm, and the length of the fiber is 2-20 μm.
Further, the organic monomer comprises one or more of acrylamide and N-methylol acrylamide.
Further, the cross-linking agent is N, N' -methylene bisacrylamide.
Further, the dispersing agent is one or more of ammonium polyacrylate, polymethacrylic acid and castor oil.
Further, the ceramic powder is Y 2 O 3 A stable tetragonal phase, preferably ZrO 2 Powder of Al 2 O 3 And (3) powder.
Further, a catalyst can be added into the raw materials, wherein the catalyst is N, N, N ', N' -tetramethylethylenediamine, and the catalyst accounts for 0.02-1 part by weight.
The method has the advantages that the pore-forming agent and the ceramic fibers are added, wherein the pore-forming agent and the ceramic fibers can generate a space occupying effect, so that sintering shrinkage of raw materials caused by low solid phase content in a water-based gel injection molding method is prevented, and the generation of defects such as cracking of the raw materials can be reduced due to the skeleton, bridging and the like of the ceramic fibers. The porosity of the porous ceramic material is obviously improved and the defects of deformation, cracking and the like of the porous ceramic material are greatly reduced under the action of the pore-forming agent and the ceramic fiber in the raw material sintering. Meanwhile, the PMMA microspheres adopted by the invention can be cracked and removed in the binder removal link, and can form a macroporous-mesoporous structure after being sintered.
According to another aspect of the present invention, there is provided a method for preparing a high porosity porous ceramic material, comprising the steps of:
s1, mixing and grinding a water-based solution, ceramic powder, a dispersing agent, a pore-forming agent and ceramic fibers to form a premixed solution;
s2, adding an initiator into the premixed solution, and injecting the premixed solution into a mold to form a wet blank;
s3, demolding the wet blank, and sintering to obtain a porous ceramic material with porosity of more than 70%;
wherein the mixing proportion of the premixed liquid is as follows according to parts by weight: 44.4 to 76.5 portions of water-based solution, 10 to 30 portions of ceramic powder, 0.1 to 1 portion of dispersant, 1 to 8 portions of pore-forming agent, 1 to 6 portions of ceramic fiber and 1 to 5 portions of initiator.
Further, the grinding is ball milling, and the ball milling time is 12-24h; the ball milling tank used for ball milling treatment is a nylon or alumina ball milling tank; the ball grinding balls are agate balls or silicon nitride balls or polyurethane balls; the rotating speed of the ball mill is 50-200 r/min.
Further, the water-based solution, the ceramic powder and the dispersing agent are firstly subjected to primary ball milling treatment, the pore-forming agent and the ceramic fiber are added after the ball milling treatment is finished, the ball milling treatment is carried out again, and the step S2 is carried out after the ball milling treatment is finished twice.
Further, in the step S2, a catalyst may be added, wherein the catalyst is N, N' -tetramethylethylenediamine, and the catalyst is 0.02 to 1 part by weight.
Further, the water-based solution comprises water, an organic monomer, a cross-linking agent,
wherein the mixing proportion of the water-based solution is as follows according to the parts by weight: 40 to 60 portions of water, 4 to 15 portions of organic monomer and 0.4 to 1.5 portions of cross-linking agent.
Further, the water is preferably deionized water.
Further, the pore-forming agent is PMMA microspheres, and the particle size D50 of the microspheres is 10-50 μm.
Further, the initiator includes one or more of ammonium sulfate, sodium persulfate, and potassium persulfate.
Furthermore, the ceramic fiber is alumina fiber or boron nitride fiber, the diameter of the fiber is 0.5-5 μm, and the length of the fiber is 2-20 μm.
Further, the organic monomer comprises one or more of acrylamide and N-methylol acrylamide.
Further, the cross-linking agent is N, N' -methylene-bis-acrylamide.
Further, the dispersing agent is one or more of ammonium polyacrylate, polymethacrylic acid and castor oil.
Further, the ceramic powder is Y 2 O 3 A stable tetragonal phase, preferably, zrO 2 Powder of Al 2 O 3 And (3) powder.
Further, the solid phase volume content of the ceramic powder of the premixed liquid is 5-25%.
Further, the mold is coated with a release agent, the mold is a polytetrafluoroethylene mold or a polypropylene mold, and the release agent is one or more of vaseline, silicone oil and methyl silicone oil
Further, the wet blank demoulding and sintering are divided into three stages:
(1) Pretreatment: the wet blank is cured in a water bath and demoulded,
wherein the water bath temperature is 40-80 deg.C, and the time is 30-120min;
(2) Pre-sintering: sintering the wet blank at a low temperature of 30-50 ℃ for 24-80h;
or
Freeze-drying the wet blank, and vacuum-drying, wherein the freeze-drying temperature is-80 to-40 ℃, and the time is 8 to 12 hours; the vacuum drying is to vacuumize to below 10pa for 24-120h;
(3) And (3) sintering: and (3) sintering the wet blank, heating to 450-600 ℃ at the heating rate of 0.2-0.5 ℃/min for glue discharging for 60-180 minutes, then heating to 1200-1600 ℃ at the heating rate of 5-10 ℃/min, and keeping for 60-180 minutes.
Compared with the prior art, the invention has the advantages and beneficial effects that the invention is based on the water-based gel injection molding method, the pore-forming agent and the ceramic fiber are added in the raw stock formula, wherein the pore-forming agent and the ceramic fiber can generate space occupying effect, the sintering shrinkage of a wet blank in the water-based gel injection molding method caused by low solid phase content is prevented, and the generation of defects such as cracking of the wet blank can be reduced due to the skeleton, bridging and the like of the ceramic fiber. The porosity of the porous ceramic material is obviously improved and the defects of deformation, cracking and the like are greatly reduced through the function of sintering the pore-forming agent and the ceramic fiber in the raw materials. Meanwhile, the PMMA microspheres adopted by the invention can be cracked and removed in the binder removal link, and can form a macroporous-mesoporous structure after being sintered. Meanwhile, after sintering, the added ceramic fiber can form a bridging structure in the porous ceramic, so that the mechanical property of the porous ceramic material is improved. Meanwhile, the invention is based on a water-based gel injection molding method, can realize in-situ and near-net-size molding and can directly prepare a blank with a complex shape.
Due to the technical scheme provided by the invention, the problems that the green body shrinks and cracks when the wet green body of the porous ceramic material is dried, the green body of the porous ceramic material excessively shrinks and cracks when the green body is sintered, the porosity cannot be effectively kept and the like are solved.
Drawings
FIG. 1 is a graph of a sample without additions from example 1.
FIG. 2 shows Al addition in example 1 2 O 3 Sample drawing of fibers.
FIG. 3 is a diagram of a sample to which PMMA microspheres were added in example 1.
FIG. 4 shows the addition of PMMA microspheres and Al in example 1 2 O 3 Sample drawing of fibers.
FIG. 5 is a partially enlarged view of the CT scan profile and the SEM of example 3.
FIG. 6 is a plot of the compressive strength of the samples of example 3.
Detailed Description
In order to better understand the technical scheme of the invention, the invention is further explained by combining the specific embodiment and the attached drawings of the specification.
Example 1: adding pore-forming agent and ceramic fiber, and comparing the samples without adding pore-forming agent and ceramic fiber.
To verify the effect of the pore former and ceramic fibers on the wet green, four sets of samples were prepared as follows. The preparation process comprises the following steps:
stirring and mixing 500g of deionized water, 60g of acrylamide and 6g of N, N' -methylene-bisacrylamide to form a water-based solution; the aqueous solution was mixed with 200g of ZrO 2 Mixing the powder with 3g of ammonium polyacrylate, and ball-milling for 12 hours at the speed of 100 revolutions per minute to obtain slurry;
the obtained slurry was divided into four equal portions, and sample 1, sample 2, sample 3, and sample 4 were numbered, respectively. The raw materials were further added according to the following formulation and ball milled for 12h at 100 rpm.
20.5g of a 20% by weight aqueous ammonium persulfate solution and 2g of N, N' -tetramethylethylenediamine were added to the above four samples, and the mixture was sufficiently stirred and then poured into silicone oil-coated polypropylene molds having a size of 145 mm. Times.145 mm. Times.70 mm and a mold thickness of 20mm; curing the mould in a water bath at 55 ℃; removing the wet blank which is cured and cooled to room temperature from the mold; the wet blank is dried by adopting a vacuum freeze drying process, and the vacuum freeze drying process comprises the following steps: freezing at-60 deg.C for 10h, vacuumizing to 10Pa, and maintaining for 24h to obtain four samples with photographs shown in figures 1-4 of the specification.
As shown in figures 1-4 of the specification:
the sample without the additive has large crack fracture, the surface is full of cracked small cracks, the drying shrinkage is large, the shrinkage is uneven, and the sample deforms.
Addition of Al only 2 O 3 The shrinkage deformation of the sample is improved by the fiber or PMMA microsphere, but the generation of cracks cannot be completely avoided.
With addition of Al 2 O 3 The fiber and PMMA microsphere samples have no large cracks on the blank and no small cracks on the surface.
The addition of an appropriate amount of Al to be used in the present invention is explained 2 O 3 The fiber and PMMA microsphere can form a support framework, and the drying shrinkage and cracking of the low solid content gel injection molding wet blank are greatly reduced.
Example 2: determination of the content of ceramic fibres
Slurries were formulated as described above in example 1. The obtained slurry was divided equally into 5 parts based on ZrO 2 The mass ratio of the powder is 0%, 5%,8%,15% and 18% by adding ceramic fiber respectively. Five samples were each ball milled for 12h at 50 rpm.
Adding 20.5g of 20% by weight aqueous ammonium persulfate solution and 2g of N, N' -tetramethylethylenediamine into the above five samples, stirring them sufficiently, and pouring them into silicone oil-coated polypropylene molds having a size of 145 mm. Times.145 mm. Times.70 mm and a mold thickness of 20mm; curing the mould in a water bath at 55 ℃; removing the wet blank with the curing finished and the temperature reduced to room temperature from the mold; the wet blank is dried by adopting a vacuum freeze drying process, and the vacuum freeze drying process comprises the following steps: freezing at-60 deg.C for 8h, vacuumizing to 10Pa, and maintaining for 24h. A dry green body is obtained. And (3) putting the blank into a high-temperature furnace, heating to 600 ℃ at the heating rate of 0.5 ℃/min for discharging glue for 2h, then heating to 1500 ℃ at the heating rate of 5 ℃/min, keeping for 120min, and then cooling along with the furnace to obtain a porous ceramic material sample.
The results of the test on the sintering shrinkage of the different samples are shown in the following table.
| Ceramic fiber content/%) | 0 | 5 | 8 | 15 | 18 |
| Shrinkage/% of the sintering line | 46.28 | 28.19 | 16.25 | 11.34 | 10.67 |
It can be seen that the shrinkage reached more than 46% after sintering of the wet green without adding ceramic fibers to the slurry, and a high porosity material could not be obtained; according to ZrO 2 Firing of green body with ceramic fiber added in amount of 5% by mass of powderThe shrinkage after the sintering is reduced to about 28 percent, and when the addition amount of the ceramic fiber is ZrO 2 When the powder mass is 8%, the sintering shrinkage is reduced to about 16%. When the addition amount of the ceramic fiber is too small, the inhibition effect on sintering shrinkage is relatively small, but when the addition amount of the ceramic fiber is too large, the mechanical property of the porous ceramic material is influenced, the heat conductivity coefficient of the porous ceramic material is improved, and the manufacturing cost of the material is greatly improved. Thus, the experiment proves that ZrO was transformed 2 The proper content of the ceramic fiber added in the powder is 8-15% of the mass of the zirconia powder, namely 1-6 parts by weight of the ceramic fiber.
Example 3:
in this example, the organic monomer is acrylamide, the crosslinking agent is N, N ' -methylenebisacrylamide, the dispersant is ammonium polyacrylate, the catalyst is N ', N ' -tetramethylethylenediamine, and the initiator is ammonium persulfate.
The preparation process comprises the following steps:
307g of deionized water, 44.4g of acrylamide and 4.4g of N, N' -methylenebisacrylamide are mixed together and fully stirred until a clear and transparent solution (namely a water-based solution) is obtained; the aqueous solution, 145g ZrO 2 Mixing the powder with 3g of ammonium polyacrylate and carrying out ball milling for 12 hours to obtain slurry;
adding 21.7g of PMMA microspheres and 14.5g of alumina fibers into the obtained slurry, and carrying out ball milling for 12 hours at the speed of 100 revolutions per minute to obtain a premixed solution;
adding 20.5g of a 20% by weight aqueous ammonium persulfate solution and 2g of N, N' -tetramethylethylenediamine to the resulting premixed solution, sufficiently stirring them, and then rapidly pouring them into a silicone oil-coated polypropylene mold having a mold size of 135 mm. Times.135 mm. Times.70 mm and an injection molding thickness of 30mm; curing the mould in a water bath at 55 ℃; removing the wet blank which is cured and cooled to room temperature from the mold;
putting the wet blank into an oven, and drying for 48 hours at 40 ℃ to obtain a dried blank body; and (3) putting the dry blank into a high-temperature furnace, slowly heating to 500 ℃ at the speed of 0.25 ℃/min for discharging glue for 2h, then heating to 1400 ℃ at the speed of 10 ℃/min, preserving heat for 1.5h, cooling along with the furnace, and finishing sintering.
Measure the implementationThe porosity of the porous ceramic material, namely the zirconia-based porous heat-insulating material prepared by the embodiment can reach 82.1 percent, and the volume density is 0.98g/cm -3 And the compressive strength is more than 5MPa, and the light weight and high strength performance is achieved. The thermal conductivity of the material is tested by a flash method, the thermal conductivity of the zirconia-based porous thermal insulation material of the embodiment is 0.07W/m.k, the thermal conductivity reaches the standard of the thermal insulation material, and the thermal insulation performance of the material is far better than that of a common thermal insulation material corundum light refractory brick (the thermal conductivity is 0.5W/m.k-1.0W/m.k).
Fig. 2 of the invention is a microscopic morphology result obtained by the CT and scanning electron microscope observation in this embodiment, which shows that the porous ceramic material prepared by the present invention exhibits a mesoporous-macroporous composite structure.
Figure 3 of the invention the sample compression strength curve of this example was used. The sample has the maximum compression strength of 12.6MPa under the condition that the porosity reaches 82.1 percent, and is a light high-strength heat insulating material. The added ceramic fiber and the mesoporous-macroporous composite structure presented by the sample can help the porous ceramic material sample to greatly improve the strength.
Example 4
In this example, the organic monomer was N-methylolacrylamide, the crosslinking agent was N, N ' -methylenebisacrylamide, the dispersing agent was polymethacrylic acid, the catalyst was N, N, N ', N ' -tetramethylethylenediamine, and the initiator was sodium persulfate in an amount of 20% by weight.
The preparation process is carried out as follows:
291g of deionized water, 38g of N-methylolacrylamide and 3g of N, N' -methylenebisacrylamide are mixed together and sufficiently stirred until a clear and transparent solution (namely a water-based solution) is obtained; the aqueous solution, 163g ZrO 2 Mixing and ball-milling the powder and 5g of polymethacrylic acid for 24 hours; obtaining slurry;
adding 29g of PMMA microspheres and 17.4g of boron nitride fibers into the obtained slurry, and carrying out ball milling for 12 hours at the speed of 70 r/min to obtain a premixed solution;
to the resulting premix was added 15.2g of a 20% by weight aqueous solution of sodium persulfate and 1.5g of N, N' -tetramethylethylenediamine, followed by sufficient stirring, and then, immediately poured into a polytetrafluoroethylene mold coated with a silicone oil as a mold release agent, the mold having a diameter of 166 mm. Times.166 mm. Times.60 mm and an injection thickness of 30mm; placing the mould in a water bath at 60 ℃ for curing; removing the wet blank which is cured and cooled to room temperature from the mold;
putting the wet blank into a cold trap of a vacuum freeze dryer, freezing for 10h at-80 ℃, then vacuumizing to 5pa, and keeping for 120h to obtain a dry blank; and (3) putting the dry blank into a high-temperature furnace, slowly heating to 550 ℃ at the speed of 0.2 ℃/min for glue discharging for 2h, then heating to 1550 ℃ at the speed of 5 ℃/min, preserving heat for 2h, furnace cooling, and finishing sintering.
The porosity of the porous ceramic material, namely the zirconia-based porous heat-insulating material prepared by the embodiment can reach 75.6%, and the volume density is 1.34g/cm -3 And the compressive strength is greater than 6MPa, and the light weight and high strength performance is achieved. The thermal conductivity of the material was measured by a flash method, and the thermal conductivity of the porous zirconia-based thermal insulation material of this example was 0.09W/m.k, which is a thermal insulation material. In particular, the sample of this example showed only 2.1% shrinkage at 1700 ℃ using 1h line, and had extremely high dimensional stability.
Example 5
The preparation process comprises the following steps:
mixing 400g of deionized water, 40g of acrylamide and 4g of N, N' -methylene bisacrylamide together, and fully stirring until a clear and transparent solution (namely a water-based solution) is obtained; the aqueous solution, 100g ZrO 2 Mixing and ball-milling the powder and 1g of polymethacrylic acid for 12 hours; obtaining slurry;
adding 10g of PMMA microspheres and 10g of boron nitride fibers into the obtained slurry, and carrying out ball milling at the speed of 50 revolutions per minute for 12 hours to obtain a premixed solution;
adding 10g of sodium persulfate and 0.2g of N, N' -tetramethylethylenediamine into the obtained premixed solution, fully stirring, quickly pouring into a polytetrafluoroethylene mold coated with release agent methyl silicone oil, wherein the diameter size of the mold is 80mm multiplied by 60mm, and the injection molding thickness is 30mm; placing the mould in a water bath at 40 ℃ for curing for 30min; removing the wet blank with the curing finished and the temperature reduced to room temperature from the mold;
putting the wet blank into a cold trap of a vacuum freeze dryer, freezing for 8 hours at-80 ℃, then vacuumizing to 10pa, and keeping for 24 hours to obtain a dried blank; and (3) putting the dry blank into a high-temperature furnace, slowly heating to 450 ℃ at the speed of 0.2 ℃/min for glue discharging for 1h, then heating to 1200 ℃ at the speed of 5 ℃/min, preserving heat for 1h, cooling along with the furnace, and finishing sintering.
The porosity of the porous ceramic material prepared by the embodiment can reach 77.4%, and the volume density is 1.14g/cm -3 The compression strength is more than 5MPa, and the light weight and high strength performance is achieved. The thermal conductivity of the material was measured by the flash method, and the thermal conductivity of the porous zirconia-based thermal insulation material of this example was 0.08W/m.k, which is a thermal insulation material.
Example 6
The preparation process comprises the following steps:
mixing 600g of deionized water, 150g of N-methylolacrylamide and 15g of N, N' -methylenebisacrylamide together, and fully stirring until a clear and transparent solution (namely a water-based solution) is obtained; mixing the water-based solution with 300g of Al 2 O 3 Mixing the powder with 10g of castor oil, and ball-milling for 12 hours; obtaining slurry;
adding 80g of PMMA microspheres and 60g of alumina fibers into the obtained slurry, and carrying out ball milling at the speed of 200 revolutions per minute for 24 hours to obtain a premixed solution;
adding 50g of potassium persulfate and 10g of N, N' -tetramethylethylenediamine into the obtained premixed solution, fully stirring, quickly pouring into a polypropylene mould coated with a release agent vaseline, wherein the diameter of the mould is 80mm multiplied by 60mm, and the injection thickness is 30mm; placing the mould in a water bath at 80 ℃ for curing for 120min; removing the wet blank with the curing finished and the temperature reduced to room temperature from the mold;
putting the wet blank into a cold trap of a vacuum freeze dryer, freezing for 12h at-40 ℃, then vacuumizing to 10pa, and keeping for 120h to obtain a dried blank; and (3) putting the dry blank into a high-temperature furnace, slowly heating to 600 ℃ at the speed of 0.5 ℃/min for glue discharging for 3h, then heating to 1600 ℃ at the speed of 10 ℃/min, preserving heat for 3h, cooling along with the furnace, and finishing sintering.
The porosity of the porous ceramic material prepared by the embodiment can reach 80.4%, and the volume density is 0.94g/cm -3 The compression strength is more than 5MPa, and the light weight and high strength performance is achieved. Testing of material guides by flash methodThe thermal conductivity of the porous zirconia-based heat insulating material of the present example was 0.06W/m.k, which is a heat insulating material.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the features described above have similar functions to (but are not limited to) those disclosed in this application.
Claims (6)
1. A method for preparing a high-porosity porous ceramic material is characterized by comprising the following steps:
s1, mixing and grinding a water-based solution, ceramic powder, a dispersing agent, a pore-forming agent and ceramic fibers to form a premixed solution;
s2, adding an initiator into the premixed liquid, and injecting the premixed liquid into a mold to form a wet blank;
s3, demolding and sintering the wet blank to obtain a porous ceramic material with porosity of more than 70%;
wherein the mixing proportion of the premix is as follows according to parts by weight: 44.4-76.5 parts of water-based solution, 10-30 parts of ceramic powder, 0.1-1 part of dispersant, 1-8 parts of pore-forming agent, 1-6 parts of ceramic fiber and 1-5 parts of initiator;
the water-based solution comprises water, an organic monomer and a cross-linking agent;
the pore-forming agent is PMMA microspheres, and the particle size of the PMMA microspheres is D50 which is 10-50 mu m;
the ceramic fiber is boron nitride fiber or alumina fiber, the fiber diameter is 0.5-5 μm, and the fiber length is 2-20 μm;
the wet blank demoulding and sintering are divided into three stages:
(1) Pretreatment: the wet blank is cured in a water bath and demoulded,
wherein the water bath temperature is 40-80 deg.C, and the time is 30-120min;
(2) Pre-sintering: sintering the wet blank at a low temperature of 30-50 ℃ for 24-80h;
or, the wet blank is dried by adopting a vacuum freeze drying process, wherein the vacuum freeze drying process comprises the following steps: freezing at-80 to-40 ℃ for 8 to 12 hours; then vacuumizing to below 10pa, and keeping for 24-120h;
(3) And (3) sintering: and (3) sintering the wet blank, heating to 450-600 ℃ at the heating rate of 0.2-0.5 ℃/min, discharging the glue for 60-180 minutes, heating to 1200-1600 ℃ at the heating rate of 5-10 ℃/min, and keeping for 60-180 minutes.
2. The method for preparing the high-porosity porous ceramic material according to claim 1, wherein the mixing ratio of the water, the organic monomer and the cross-linking agent is as follows according to parts by weight: 40 to 60 portions of water, 4 to 15 portions of organic monomer and 0.4 to 1.5 portions of cross-linking agent.
3. The method of claim 1, wherein said porous ceramic material is sintered to a porosity of greater than 70% and a bulk density of less than 1.4g/cm 3 The compressive strength is more than 5MPa; testing the thermal conductivity coefficient of the material by a flash method, wherein the thermal conductivity coefficient of the porous ceramic material is less than 0.1W/(m.k); the porous ceramic material has a mesoporous-macroporous composite structure.
4. The method for preparing a high porosity porous ceramic material according to claim 1 wherein the initiator comprises one or more of ammonium sulfate, sodium persulfate and potassium persulfate.
5. The method of claim 1, wherein the organic monomer comprises one or more of acrylamide, N-methylolacrylamide; the cross-linking agent is N, N' -methylene-bisacrylamide; the dispersant is one or more of ammonium polyacrylate, polymethacrylic acid and castor oil.
6. The method of claim 1, wherein the mold is coated with a release agent, the mold is a polytetrafluoroethylene mold or a polypropylene mold, and the release agent is one or more of vaseline, silicone oil, and methyl silicone oil.
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| 热裂解多孔陶瓷球负载催化剂制备及物性研究;毕冬梅等;《华中科技大学学报(自然科学版)》;20151223(第12期);全文 * |
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