CN111807852A - Method for preparing high-porosity porous ceramic material - Google Patents
Method for preparing high-porosity porous ceramic material Download PDFInfo
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- CN111807852A CN111807852A CN202010686548.1A CN202010686548A CN111807852A CN 111807852 A CN111807852 A CN 111807852A CN 202010686548 A CN202010686548 A CN 202010686548A CN 111807852 A CN111807852 A CN 111807852A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000835 fiber Substances 0.000 claims abstract description 58
- 239000000919 ceramic Substances 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 15
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 6
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229940099259 vaseline Drugs 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 abstract description 18
- 238000005336 cracking Methods 0.000 abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 23
- 238000000498 ball milling Methods 0.000 description 18
- 239000002002 slurry Substances 0.000 description 13
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 9
- 239000012774 insulation material Substances 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
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- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- 239000004677 Nylon Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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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 the 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 the various methods for preparing porous ceramic materials, the gel-casting 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 becomes 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 solvent cost, environmental pollution caused by 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, by weight, 44.4-76.5 parts of a water-based solution, 10-30 parts of ceramic powder, 0.1-1 part of a dispersing agent, 1-8 parts of a pore-forming agent, 1-6 parts of ceramic fiber and 1-5 parts of an 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: 40-60 parts of water, 4-15 parts of organic monomer and 0.4-1.5 parts 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-3The compressive strength is more than 5 MPa; 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, and the size of the porous ceramic material is larger than 80 multiplied by 80mm or the diameter is larger than 80 mm.
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 of the microspheres D50 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 Y2O3A stable tetragonal phase, preferably ZrO2Powder of Al2O3And (3) powder.
Further, a catalyst can be added into the raw materials, wherein the catalyst is N, N, N ', N' -tetramethylethylenediamine, and the weight portion of the catalyst is 0.02-1.
The method has the advantages and beneficial effects that the pore-forming agent and the ceramic fiber are added, wherein the pore-forming agent and the ceramic fiber can generate space occupying effect, so that sintering shrinkage of the raw material 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 material can be reduced due to the skeleton, bridging and other effects of the ceramic fiber. 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 the water-based solution, the ceramic powder, the dispersant, the pore-forming agent and the ceramic fiber 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 the wet blank, and sintering 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 dispersing agent, 1-8 parts of pore-forming agent, 1-6 parts of ceramic fiber and 1-5 parts of initiator.
Further, the grinding is ball milling, and the ball milling time is 12-24 h; 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 dispersant 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 weight portion of the catalyst is 0.02 to 1 portion.
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: 40-60 parts of water, 4-15 parts of organic monomer and 0.4-1.5 parts of cross-linking agent.
Further, the water is preferably deionized water.
Further, the pore-forming agent is PMMA microspheres, and the particle size of the microspheres D50 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 bisacrylamide.
Further, the dispersing agent is one or more of ammonium polyacrylate, polymethacrylic acid and castor oil.
Further, the ceramic powder is Y2O3A stable tetragonal phase, preferably, ZrO2Powder of Al2O3And (3) powder.
Further, the solid phase volume content of the ceramic powder of the premixed liquid is 5-25%.
Further, the mould is coated with a release agent, the mould is a polytetrafluoroethylene mould or a polypropylene mould, 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 30-120 min;
(2) pre-sintering: sintering the wet blank at a low temperature of 30-50 ℃ for 24-80 h;
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 24-120 h;
(3) and (3) sintering: the wet blank is sintered, the temperature is raised to the temperature of 450-600 ℃ at the heating rate of 0.2-0.5 ℃/min for glue removal for 60-180 minutes, and then the temperature is raised to the temperature of 1200-1600 ℃ at the heating rate of 5-10 ℃/min for holding 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 generation of defects such as deformation, cracking and the like is greatly reduced through 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. 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 additives in example 1.
FIG. 2 shows the addition of Al in example 12O3Sample 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 12O3Sample 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 the pore-forming agent and the 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 N, N' -methylene bisacrylamide to form a water-based solution; the aqueous solution was mixed with 200g of ZrO2Mixing 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 portions and numbered sample 1, sample 2, sample 3, and sample 4, respectively. The raw materials were further added according to the formulation of the following table and ball milled at 100 rpm for 12 h.
Respectively adding 20.5g of 20 percent wt ammonium persulfate aqueous solution and 2g N, N, N ', N' -tetramethyl ethylene diamine into the four samples, fully stirring, quickly pouring into a polypropylene mould coated with silicone oil, wherein the size of the mould is 145mm multiplied by 70mm, and the injection molding thickness is 20 mm; 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 as 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 only2O3The 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 Al2O3The 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 explained2O3The fiber and PMMA microsphere can form a supporting framework, and the drying shrinkage and cracking of the gel injection molding wet blank with low solid content are greatly reduced.
Example 2: determination of the content of ceramic fibres
Slurries were prepared according to the formulation described above in example 1. The obtained slurry was divided equally into 5 parts based on ZrO2The mass ratio of the powder is 0%, 5%, 8%, 15% and 18% by adding ceramic fiber respectively. Five samples were ball milled for 12h at 50 rpm.
20.5g of 20 wt% ammonium persulfate aqueous solution and 2g N, N, N ', N' -tetramethylethylenediamine are respectively added into the five samples, and the mixture is fully stirred and then is quickly poured into a polypropylene mould coated with silicone oil, wherein the size of the mould is 145mm multiplied by 70mm, and the injection molding thickness is 20 mm; 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 8h, vacuumizing to 10Pa, and maintaining for 24 h. 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.
| Content of ceramic fiber/%) | 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 ZrO2The shrinkage of the green body added with ceramic fiber is reduced to about 28 percent after sintering, when the mass of the powder is 5 percent, and the addition amount of the ceramic fiber is ZrO2When 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 is easily obtained2The 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 embodiment, 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 is carried out as follows:
307g of deionized water, 44.4g of acrylamide and 4.4g of 4.4g 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, 145g ZrO2Mixing 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 20 wt% ammonium persulfate aqueous solution and 2g N, N, N ', N' -tetramethyl ethylene diamine into the obtained premix, fully stirring, quickly pouring into a polypropylene mould coated with silicone oil, wherein the mould size is 135mm multiplied by 70mm, and the injection molding thickness is 30 mm; 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.
The porosity of the porous ceramic material prepared by the embodiment, namely the zirconia-based porous heat-insulating material, can reach 82.1 percent, and the volume density is 0.98g/cm-3The compression 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 present invention is a microstructure result obtained by the observation of the CT and the scanning electron microscope in this embodiment, which shows that the porous ceramic material prepared by the present invention has 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 is N-methylolacrylamide, the crosslinking agent is N, N '-methylenebisacrylamide, the dispersing agent is polymethacrylic acid, the catalyst is N, N' -tetramethylethylenediamine, and the initiator is sodium persulfate of 20 wt%.
The preparation process is carried out as follows:
291g of deionized water, 38g N-hydroxymethyl acrylamide3g N, N' -methylenebisacrylamide is mixed together and fully stirred until a clear and transparent solution (namely a water-based solution) is obtained; the aqueous solution, 163g ZrO2Mixing 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 at the speed of 70 r/min for 12h to obtain a premixed solution;
adding 15.2g of 20 wt% sodium persulfate aqueous solution and 1.5g of 1.5g N, N, N ', N' -tetramethylethylenediamine into the obtained premix, fully stirring, and quickly pouring into a polytetrafluoroethylene mold coated with release agent silicone oil, wherein the diameter of the mold is 166mm multiplied by 60mm, and the injection molding thickness is 30 mm; 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-3The compression strength is more than 6MPa, 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 zirconia-based porous 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 is carried out as follows:
mixing 400g of deionized water, 40g of acrylamide and 4g N, N' -methylenebisacrylamide together, and stirring the mixture fully until a clear and transparent solution (namely a water-based solution) is obtained; the aqueous solution, 100g ZrO2Mixing 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 N, N, N ', N' -tetramethylethylenediamine into the obtained premix, fully stirring, quickly pouring into a polytetrafluoroethylene mold coated with release agent methyl silicone oil, wherein the diameter of the mold is 80mm multiplied by 60mm, and the injection molding thickness is 30 mm; placing the mould in a water bath at 40 ℃ for curing for 30 min; 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 8h at-80 ℃, then vacuumizing to 10pa, and keeping for 24h 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-3The 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 zirconia-based porous thermal insulation material of this example was 0.08W/m.k, which is a thermal insulation material.
Example 6
The preparation process is carried out as follows:
mixing 600g of deionized water, 150g of N-methylolacrylamide and 15g N, N' -methylenebisacrylamide together, and stirring the mixture fully until a clear and transparent solution (namely a water-based solution) is obtained; mixing the water-based solution with 300g of Al2O3Mixing 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 N, N, N ', N' -tetramethylethylenediamine into the obtained premix, fully stirring, and rapidly pouring into a polypropylene mold coated with vaseline as a release agent, wherein the mold has a diameter of 80mm × 80mm × 60mm and an injection molding thickness of 30 mm; placing the mould in a water bath at 80 ℃ for curing for 120 min; 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 12h at-40 ℃, then vacuumizing to 10pa, and keeping for 120h to obtain a dry blank; and (3) putting the dry blank into a high-temperature furnace, slowly heating to 600 ℃ at the speed of 0.5 ℃/min for discharging glue 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-3The 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 zirconia-based porous thermal insulation material of this example was 0.06W/m.k, which is a thermal insulation 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 (10)
1. The high-porosity porous ceramic material 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.
2. The high porosity porous ceramic material of claim 1, wherein said water based solution comprises water, organic monomers, cross-linking agents,
wherein, the mixing proportion of the water, the organic monomer and the cross-linking agent is as follows according to the parts by weight: 40-60 parts of water, 4-15 parts of organic monomer and 0.4-1.5 parts of cross-linking agent.
3. The high porosity porous ceramic material of claim 1, wherein the porous ceramic material produced by sintering has a porosity of greater than 70% and a bulk density of less than 1.4g/cm-3The compressive strength is more than 5 MPa; 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 high-porosity porous ceramic material of claim 1, wherein the pore-forming agent is PMMA microspheres, and the particle size of the PMMA microspheres is D50 of 10 to 50 μm; the initiator comprises one or more of ammonium sulfate, sodium persulfate and potassium persulfate.
5. The high porosity porous ceramic material according to claim 1, wherein the ceramic fibers are alumina fibers or boron nitride fibers, the fiber diameter is 0.5-5 μm, and the fiber length is 2-20 μm.
6. The high porosity porous ceramic material according to claim 2, 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.
7. A method for preparing a high-porosity porous ceramic material is characterized by comprising the following steps:
s1, mixing and grinding the water-based solution, the ceramic powder, the dispersant, the pore-forming agent and the ceramic fiber 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 the wet blank, and sintering 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 dispersing agent, 1-8 parts of pore-forming agent, 1-6 parts of ceramic fiber and 1-5 parts of initiator.
8. The method of claim 7, wherein the aqueous 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: 40-60 parts of water, 4-15 parts of organic monomer and 0.4-1.5 parts of cross-linking agent.
9. The method of claim 7, 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.
10. The process for the preparation of a high porosity porous ceramic material according to claim 7 wherein the wet green is demolded and sintering is 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 30-120 min;
(2) pre-sintering: sintering the wet blank at a low temperature of 30-50 ℃ for 24-80 h;
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 24-120 h;
(3) and (3) sintering: the wet blank is sintered, the temperature is raised to the temperature of 450-600 ℃ at the heating rate of 0.2-0.5 ℃/min for glue removal for 60-180 minutes, and then the temperature is raised to the temperature of 1200-1600 ℃ at the heating rate of 5-10 ℃/min for holding for 60-180 minutes.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04132025A (en) * | 1990-09-20 | 1992-05-06 | Matsushita Electric Ind Co Ltd | Optical information recording medium |
| US5360662A (en) * | 1992-03-12 | 1994-11-01 | Hughes Aircraft Company | Fabrication of reliable ceramic preforms for metal matrix composite production |
| CN1456535A (en) * | 2003-05-30 | 2003-11-19 | 武汉理工大学 | Process for preparing porous ceramic by water-based gel injection moulding method |
| WO2007061457A2 (en) * | 2005-11-16 | 2007-05-31 | Geo2 Technologies, Inc. | System for extruding a porous substrate |
| US20080063833A1 (en) * | 2006-08-29 | 2008-03-13 | Beall Douglas M | High porosity thermally shock resistant ceramic structures |
| CN103058708A (en) * | 2013-01-07 | 2013-04-24 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of low-thermal-conductivity silicon-nitride-bonded silicon carbide porous ceramic |
| CN103467072A (en) * | 2013-08-27 | 2013-12-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method for light microporous corundum ceramic |
| CN104529497A (en) * | 2014-11-28 | 2015-04-22 | 西安交通大学 | Method for improving ceramic mold precision with vacuum freeze-drying technology |
| CN105175001A (en) * | 2015-09-01 | 2015-12-23 | 中国科学院重庆绿色智能技术研究院 | Ultralight closed cell foam ceramic preparation |
| CN105272223A (en) * | 2015-09-29 | 2016-01-27 | 北京中材人工晶体研究院有限公司 | Preparation method of large-size zirconia-based heat insulation material |
| CN106478077A (en) * | 2016-09-28 | 2017-03-08 | 广州凯耀资产管理有限公司 | A kind of porous thermal insulating ceramic material for building and preparation method thereof |
| CN107417288A (en) * | 2017-09-07 | 2017-12-01 | 济宁学院 | Alumina fibre enhancing nano aluminium oxide foamed ceramics and preparation method thereof |
| CN107805065A (en) * | 2017-09-26 | 2018-03-16 | 安徽华光光电材料科技集团有限公司 | A kind of method that porous heat-insulating ceramics are prepared using Bubble zirconia |
| CN107892582A (en) * | 2017-12-12 | 2018-04-10 | 中国人民解放军国防科技大学 | Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material |
| CN109694258A (en) * | 2017-10-23 | 2019-04-30 | 中国科学院金属研究所 | A kind of YSZ fiber reinforcement type γ-Y2Si2O7The preparation method of porous heat-insulating ceramics |
| CN110256059A (en) * | 2019-06-12 | 2019-09-20 | 山东工业陶瓷研究设计院有限公司 | A kind of high throughput earthenware slab film and preparation method thereof |
| CN111848209A (en) * | 2020-06-28 | 2020-10-30 | 航天材料及工艺研究所 | Normal-pressure drying nano heat-insulating material and preparation process thereof |
-
2020
- 2020-07-16 CN CN202010686548.1A patent/CN111807852B/en not_active Expired - Fee Related
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04132025A (en) * | 1990-09-20 | 1992-05-06 | Matsushita Electric Ind Co Ltd | Optical information recording medium |
| US5360662A (en) * | 1992-03-12 | 1994-11-01 | Hughes Aircraft Company | Fabrication of reliable ceramic preforms for metal matrix composite production |
| CN1456535A (en) * | 2003-05-30 | 2003-11-19 | 武汉理工大学 | Process for preparing porous ceramic by water-based gel injection moulding method |
| WO2007061457A2 (en) * | 2005-11-16 | 2007-05-31 | Geo2 Technologies, Inc. | System for extruding a porous substrate |
| US20080063833A1 (en) * | 2006-08-29 | 2008-03-13 | Beall Douglas M | High porosity thermally shock resistant ceramic structures |
| CN103058708A (en) * | 2013-01-07 | 2013-04-24 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of low-thermal-conductivity silicon-nitride-bonded silicon carbide porous ceramic |
| CN103467072A (en) * | 2013-08-27 | 2013-12-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method for light microporous corundum ceramic |
| CN104529497A (en) * | 2014-11-28 | 2015-04-22 | 西安交通大学 | Method for improving ceramic mold precision with vacuum freeze-drying technology |
| CN105175001A (en) * | 2015-09-01 | 2015-12-23 | 中国科学院重庆绿色智能技术研究院 | Ultralight closed cell foam ceramic preparation |
| CN105272223A (en) * | 2015-09-29 | 2016-01-27 | 北京中材人工晶体研究院有限公司 | Preparation method of large-size zirconia-based heat insulation material |
| CN106478077A (en) * | 2016-09-28 | 2017-03-08 | 广州凯耀资产管理有限公司 | A kind of porous thermal insulating ceramic material for building and preparation method thereof |
| CN107417288A (en) * | 2017-09-07 | 2017-12-01 | 济宁学院 | Alumina fibre enhancing nano aluminium oxide foamed ceramics and preparation method thereof |
| CN107805065A (en) * | 2017-09-26 | 2018-03-16 | 安徽华光光电材料科技集团有限公司 | A kind of method that porous heat-insulating ceramics are prepared using Bubble zirconia |
| CN109694258A (en) * | 2017-10-23 | 2019-04-30 | 中国科学院金属研究所 | A kind of YSZ fiber reinforcement type γ-Y2Si2O7The preparation method of porous heat-insulating ceramics |
| CN107892582A (en) * | 2017-12-12 | 2018-04-10 | 中国人民解放军国防科技大学 | Preparation method of carbon fiber reinforced nanoporous carbon heat-insulation composite material |
| CN110256059A (en) * | 2019-06-12 | 2019-09-20 | 山东工业陶瓷研究设计院有限公司 | A kind of high throughput earthenware slab film and preparation method thereof |
| CN111848209A (en) * | 2020-06-28 | 2020-10-30 | 航天材料及工艺研究所 | Normal-pressure drying nano heat-insulating material and preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| 毕冬梅等: "热裂解多孔陶瓷球负载催化剂制备及物性研究", 《华中科技大学学报(自然科学版)》 * |
| 裴立宅: "《高技术陶瓷材料》", 31 July 2015 * |
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