CN107311627A - A kind of preparation method of open pore micropore ceramics - Google Patents
A kind of preparation method of open pore micropore ceramics Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 132
- 239000011148 porous material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 22
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 22
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical group OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- 238000004887 air purification Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 230000001580 bacterial effect Effects 0.000 claims 1
- 238000007444 cell Immobilization Methods 0.000 claims 1
- 102000004190 Enzymes Human genes 0.000 abstract description 4
- 108090000790 Enzymes Proteins 0.000 abstract description 4
- 241000894006 Bacteria Species 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 125000005909 ethyl alcohol group Chemical group 0.000 abstract 1
- FIKFOOMAUXPBJM-UHFFFAOYSA-N hepta-2,5-dienediamide Chemical class NC(=O)C=CCC=CC(N)=O FIKFOOMAUXPBJM-UHFFFAOYSA-N 0.000 abstract 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 14
- 238000005187 foaming Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to a kind of preparation method of open pore micropore ceramics, belong to porous ceramics preparing technical field.The present invention includes following continuous preparation process：A) prepared by ceramic slurry：Under aqueous systems, prepare and include Sodium Polyacrylate, binding agent, ethylenic unsaturation monomer, N, the ceramic slurry T of N methylene-bisacrylamides, ammonium persulfate and ceramic powders；B) prepared by ceramic body：Tetramethylethylenediamine is mixed and preform with ceramic slurry T, it is 30 80 DEG C that the type body of formation, which is placed in temperature, humidity is to stablize 10 48 hours in the environment of 70 100% to obtain ceramic body；C) ceramic body dewatering process：The ceramic body of acquisition soaks 12 96 hours in water, then soaks 24 96 hours, then dries in the shade in 25 60 DEG C of absolute ethyl alcohols；D) high-sintering process：The ceramic body dried in the shade carries out high temperature sintering and removes organic principle, obtains micropore ceramics.The open pore micropore ceramics prepared by the present invention can be used for air cleaning, fixes, is fixed for bacteria adhension, or for cell for biology enzyme.
Description
Technical Field
The invention relates to a preparation method of microporous ceramics, in particular to a composition method of microporous ceramics with open pores, belonging to the technical field of ceramic preparation.
Background
The microporous ceramic is a ceramic body containing a large number of open or closed micropores in the interior or on the surface of the ceramic, and the pore size is generally in the micron or submicron order. They may consist of most ceramic powders, such as alumina, zirconia, calcium phosphate, etc. The properties and applications of microporous ceramics are directly related to the structure, diameter of the pores and whether the pores are open or not. For a closed pore, its application is limited. On the contrary, the porous ceramic is widely used for filtering various liquids and gases, immobilizing bio-enzyme carriers, and biocompatible carriers, and is particularly widely used in environmental engineering, such as treatment of industrial water, domestic water, purification of sewage, and the like. In these applications, the use of open pore microporous ceramics is in turn directly related to the pore diameter. For example, in the cell-adaptive carrier, the pore diameter is 3-10 microns, which can load and fix cells well, the small pores can not load cells into the pores, and the large pores can easily allow the cells to migrate out of the pores. For example, in the case of a carrier for loading and immobilizing a biological enzyme, too large pores tend to cause the loss of the enzyme immobilized in the pores, and thus the biological enzyme cannot be immobilized well. Therefore, the open pore microporous ceramic with the pore diameter of less than 10 microns has wide application value in the biological related field. In addition, in practical applications, the microporous ceramics are also required to have good mechanical strength. Therefore, it is of great importance to develop a technology capable of preparing a microporous ceramic having a high mechanical strength and uniform and open pores of 10 μm or less.
Several methods for preparing microporous ceramics are available. However, these methods have drawbacks. For example, microporous ceramics prepared using the foaming process (chinese patent nos. 200410096287.9, 200510021620.4, 200610020320.9) and porogen template process (chinese patent nos. 200710016725.X, 03135581.1, 201110458811.2, 201610063506.6) have pores that are mostly closed pores and pores with large diameters (between 100 and 1000 microns). The characteristics of these pores limit their applicability. And the mechanical strength of the ceramics prepared by the foaming method is low.
The pores of the microporous ceramic prepared using the organic porogen (chinese patent No. 201510850673.0) are closed pores, and the porous ceramic prepared therefrom has poor mechanical strength and cannot be mass-produced.
The pores prepared by the freeze-drying method (chinese patent No. 200510120569.2) are closed pore structures, and the pore structures are not easy to control. In addition, the use of this method requires a low-temperature freeze-drying process for the ceramic body, which requires a large amount of energy and high manufacturing costs.
Although the pores prepared by the organic foam impregnation method (Chinese patent No. 200510043159.2, 200610013334.8) are open pores, the mechanical strength of the ceramics prepared by the method is extremely low, and the pores are all larger than 100 micrometers. This limits their use as engineering ceramics.
The ceramic prepared using the pores constructed between the ceramic particles and using the low-temperature sintering natural pore-forming method (chinese patent No. 201110154051.6) has good open pores, and the pores are between 0.1 and 2 μm. However, low-temperature sintering causes poor ceramic formation of the ceramic, so that the mechanical strength of the ceramic is extremely low, and ceramic particles are easy to fall off in the using process.
The ceramic prepared by the porous layer alternate lamination molding method (chinese patent No. 201019114034.2) has large and small pores, and the yield using this method is low, which is not suitable for mass production.
Therefore, the existing technology has not been able to satisfy the preparation technology of the microporous ceramic having the uniform and open pores of 10 μm or less while having the high mechanical strength.
Disclosure of Invention
In order to obtain a microporous ceramic having a high mechanical strength and uniform and open pores of less than 10 μm, the present invention proposes a method for preparing a microporous ceramic using the following successive steps:
A) preparing ceramic slurry: preparing ceramic slurry T containing sodium polyacrylate, a binder, an unsaturated olefin monomer, N-methylene-bisacrylamide, ammonium persulfate and ceramic powder in a water system;
B) preparing a ceramic blank: mixing tetramethylethylenediamine with the ceramic slurry T and performing the mixture to form a molded body, and placing the molded body in an environment with the temperature of 30-80 ℃ and the humidity of 70-100% for stabilization for 10-48 hours to obtain a ceramic blank;
C) a ceramic body dewatering process: soaking the obtained ceramic blank in water for 12-96 hours, then soaking in absolute ethyl alcohol at 25-60 ℃ for 24-96 hours, and then drying in the shade;
D) and (3) high-temperature sintering process: and (4) sintering the dried ceramic blank in the shade at high temperature to remove organic components to obtain the microporous ceramic.
In the step A), the ceramic slurry T has a water content of 20-60% by weight;
the ceramic slurry T comprises, by weight, 1% -5% of sodium polyacrylate, 0.5% -10% of binder, and 12% -50% of unsaturated olefin monomer and ceramic powder respectively;
the ceramic slurry T comprises, by weight, 1% -10% of N, N-methylene-bisacrylamide, and the ratio of ammonium persulfate to an unsaturated olefin monomer is 0.5% -4%;
the binder is hydroxypropyl methylcellulose, polyvinyl alcohol, polyethylene glycol or a composition formed by mixing the hydroxypropyl methylcellulose, the polyvinyl alcohol and the polyethylene glycol;
the ceramic powder is alumina, zirconia or hydroxyapatite;
the unsaturated alkene monomer is one or more of acrylic acid, methacrylic acid, acrylate, acrylamide, methacrylamide and acrylamide derivatives. Methacrylamide and methacrylic acid are preferred, and methacrylamide is more preferred.
In the step B), the ratio of the tetramethylethylenediamine to the unsaturated olefin monomer in the ceramic slurry T is 0.5-4% by weight.
The total porosity of the ceramic formed by the sintered microporous ceramic is within the range of 25-50%;
the average pore diameter of the microporous ceramic is 0.1-10 microns.
The pore diameter distribution of the microporous ceramic is narrow. In order to evaluate the uniformity of Pore diameters of microporous ceramics, in a specific experiment, hydroxyapatite microporous ceramics were prepared using hydroxyapatite powder as a starting material and tested using a Hitachi S-4800 electron scanning electron microscope and a micromeritics Auto Pore IV9500 mercury porosimeter, and the Pore diameter distribution was narrow as shown in fig. 1 and 3.
The microporous ceramic has good mechanical strength. In order to evaluate the mechanical strength of the microporous ceramic, in a specific experiment, hydroxyapatite microporous ceramic blocks having an average pore size of 1.2 μm, a total porosity of 35%, and a length, a width and a height of 2 cm were prepared as test samples using hydroxyapatite powder as a starting material, while solid hydroxyapatite ceramic and commercially available porous hydroxyapatite ceramic prepared by gas foaming were used as control test samples, and the mechanical strength of the samples was tested using an Instron5569 electronic universal material testing machine, as a result, see fig. 4, the mechanical strength of the microporous ceramic prepared by the present invention was much higher than that of the porous ceramic prepared by gas foaming and was close to that of the solid hydroxyapatite ceramic.
The invention has the following characteristics and beneficial technical effects:
the present invention provides a number of uses for microporous ceramics made by the methods of the invention, such as providing air purification, particularly for PM2.5 air pollution (e.g., when the microporous ceramic is made of alumina), for industrial liquid catalytic support (particularly formed of alumina, can support metal catalysts), for filtration containing nanoparticles, for immobilization as a bio-enzyme (e.g., microporous ceramics formed of alumina or calcium phosphate can immobilize and enhance the biological activity of different bio-enzymes), or for cell or bacteria immobilization (e.g., microporous ceramics formed of alumina or calcium phosphate).
Description of the drawings:
FIG. 1 is an SEM photograph of a microporous hydroxyapatite ceramic formed according to example 1 of the present invention;
FIG. 2 is an SEM photograph of a microporous alumina ceramic constructed according to example 2 of the present invention;
fig. 3 is mercury intrusion test results of pore diameter distribution of the microporous hydroxyapatite ceramic constructed in example 1 of the present invention;
fig. 4 shows the mechanical test results of the microporous hydroxyapatite ceramic, the solid hydroxyapatite ceramic and the hydroxyapatite ceramic prepared by commercial foaming according to example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention in any way.
The same reference numbers will be used in different drawings to identify the same or similar features.
In the present invention, the average pore diameter is the result according to the mercury intrusion test.
Example 1
In the first step a) of the present invention, 2.5 g of hydroxyapatite powder, 0.05 g of sodium polyacrylate, 0.1 g of hydroxypropyl methylcellulose as a binder, 0.5 g of an unsaturated olefin monomer methacrylamide, 0.02 g of N, N-methylene-bisacrylamide and 0.01 g of ammonium persulfate were dissolved in 2.5 g of water and thoroughly mixed to obtain a ceramic slurry T. Wherein,
the weight ratio of water in the ceramic slurry T is 44.2%;
the ratio of the sodium polyacrylate, the binder hydroxypropyl methylcellulose, the methacrylamide and the hydroxyapatite powder is respectively 2%, 4% and 20%;
the ratios of N, N-methylene-bisacrylamide, ammonium persulfate and unsaturated alkene monomer methacrylamide are respectively 4% and 2%;
in a second step B), the ceramic slurry T obtained was mixed with 0.015 g of tetramethylethylenediamine and a preform was formed. The formed molded body is stabilized at 40 ℃ for 36 hours under the protection of nitrogen to obtain a ceramic body. Wherein,
the weight ratio of the tetramethylethylenediamine to the methacrylamide in the ceramic slurry T is 3%;
in the third step C), the formed ceramic body is put into absolute ethyl alcohol to be soaked for 72 hours, and then the ceramic body is taken out to be dried in the shade at room temperature;
in the fourth step D), the dried ceramic body is sintered at 1100 ℃ for 4 hours to remove organic components, and the hydroxyapatite microporous ceramic shown in fig. 1 is obtained. The average pore diameter of the microporous ceramic is 1.2 +/-0.2 microns, as shown in figure 3, and the mechanical strength is 21 +/-2.4 MPa.
Example 2
In step A), alumina powder was used as the ceramic powder, and other production conditions were the same as in example 1;
step B) the preparation conditions were the same as in example 1;
step C) the preparation conditions were the same as in example 1;
in step D), the dried alumina ceramic body is sintered at 1600 ℃ for 5 hours to remove organic components, and the alumina microporous ceramic shown in figure 2 is obtained. The average pore diameter of the microporous ceramic is 1.4 +/-0.3 microns, and the mechanical strength is 45 +/-5.6 MPa.
Example 3
Hydroxyapatite powder of 3.5 g was used so that the ratios of sodium polyacrylate, binder hydroxypropyl methylcellulose, methacrylamide, and hydroxyapatite powder were 1.4%, 2.8%, and 14.2%, respectively, and other preparation conditions were the same as in example 1, thereby obtaining a hydroxyapatite microporous ceramic having an average pore diameter of 0.4 ± 0.1 μm and a mechanical strength of 25 ± 3.5 MPa.
Example 4
Hydroxyapatite powder of 1.5 g was used so that the ratio of sodium polyacrylate, binder hydroxypropyl methylcellulose, methacrylamide to hydroxyapatite powder was 3.3%, 6.7% and 33.3%, respectively. Other preparation conditions are the same as the example 1, and the hydroxyapatite microporous ceramic with the average pore diameter of 5.8 +/-0.7 microns and the mechanical strength of 15 +/-1.4 MPa is obtained.
Example 5
Hydroxyapatite powder was used at 1.0 gram, so that the ratio of sodium polyacrylate, binder hydroxypropyl methylcellulose, methacrylamide to hydroxyapatite powder was 5%, 10% and 50%, respectively. Other preparation conditions are the same as the example 1, and the hydroxyapatite microporous ceramic with the average pore diameter of 8.2 +/-2.7 microns and the mechanical strength of 12 +/-1.1 MPa is obtained.
Example 6
Using 1.0 g of unsaturated alkene monomer methacrylamide, and enabling the ratio of the methacrylamide to the hydroxyapatite powder to be 40%; the ratios of N, N-methylene-bisacrylamide, ammonium persulfate and methacrylamide were 2% and 1%, respectively, and other preparation conditions were the same as in example 1, to obtain hydroxyapatite microporous ceramics having an average pore diameter of 2.1. + -. 0.6. mu.m.
Example 7
A mixture was prepared using 3.5 g of water so that the specific gravity of water in the ceramic slurry T was 52.6%, and other preparation conditions were the same as in example 1, to obtain a hydroxyapatite microporous ceramic having an average pore diameter of 1.6 ± 0.5 μm.
Example 8
Hydroxyapatite microporous ceramics having an average pore diameter of 1.2. + -. 0.35 μm were obtained using 0.005 g of tetramethylethylenediamine so that the weight ratio of tetramethylethylenediamine to methacrylamide in the ceramic slurry T was 1%, and the other preparation conditions were the same as in example 1.
Example 9
Using polyvinyl alcohol as a binder, hydroxyapatite microporous ceramics having an average pore diameter of 1.2 ± 0.4 μm were obtained under the same preparation conditions as in example 1.
Example 10
Hydroxyapatite microporous ceramics having an average pore diameter of 1.2 ± 0.4 μm were obtained using polyethylene glycol as a binder under the same preparation conditions as in example 1.
Example 11
Using methacrylic acid as an unsaturated olefin monomer, hydroxyapatite microporous ceramics having an average pore diameter of 1.3. + -. 0.4. mu.m were obtained under the same preparation conditions as in example 1.
Claims (10)
1. A preparation method of open pore microporous ceramics comprises the following continuous preparation steps:
A) preparing ceramic slurry: preparing ceramic slurry T containing sodium polyacrylate, a binder, an unsaturated olefin monomer, N-methylene-bisacrylamide, ammonium persulfate and ceramic powder in a water system;
B) preparing a ceramic blank: mixing tetramethylethylenediamine with the ceramic slurry T and performing the mixture, and standing the formed molded body in an environment with the temperature of 30-80 ℃ and the humidity of 70-100% for stabilization for 10-48 hours to obtain a ceramic body;
C) a ceramic body dewatering process: soaking the obtained ceramic blank in water for 12-96 hours, then soaking in absolute ethyl alcohol at 25-60 ℃ for 24-96 hours, and then drying in the shade;
D) and (3) high-temperature sintering process: and (4) sintering the dried ceramic blank in the shade at high temperature to remove organic components to obtain the microporous ceramic.
2. The method of claim 1, wherein the ceramic slurry T in step A) has a water content of 20-60 wt%.
3. The method for preparing open-pore microporous ceramic according to claim 1, wherein the ceramic slurry T comprises, by weight, 1% -5%, 0.5% -10%, and 12% -50% of sodium polyacrylate, binder, unsaturated olefin monomer, and ceramic powder, respectively.
4. The method for preparing open-pore microporous ceramic according to claim 1, wherein the ceramic slurry T comprises, in weight percent, 1% -10% of N, N-methylene-bisacrylamide, and 0.5% -4% of ammonium persulfate and an unsaturated olefin monomer.
5. The method of claim 1, wherein the binder is hydroxypropyl methylcellulose, polyvinyl alcohol, polyethylene glycol, or a combination thereof.
6. The method of claim 1, wherein the ceramic powder is alumina, zirconia, or hydroxyapatite.
7. The method for preparing open-pore microporous ceramic according to claims 1-4, wherein the unsaturated olefin monomer is one or more of acrylic acid, methacrylic acid, acrylate, acrylamide, methacrylamide and acrylamide derivatives, preferably methacrylamide and methacrylic acid, more preferably methacrylamide.
8. The method of claim 1, wherein in step B), the ratio of tetramethylethylenediamine to the ethylenically unsaturated monomer in the ceramic slurry T is 0.5-4% by weight.
9. A microporous ceramic obtained by the method according to claims 1 to 8, wherein the microporous ceramic has an average pore diameter of 0.1 to 10 μm.
10. Use of the open pore microporous ceramic according to claim 9 for air purification, for bio-enzyme immobilization, for bacterial immobilization, or for cell immobilization.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7799839B2 (en) * | 2006-10-27 | 2010-09-21 | Korea Institute Of Machinery & Materials | Porous material having hierarchical pore structure and preparation method thereof |
| CN101955353A (en) * | 2010-09-26 | 2011-01-26 | 西安交通大学 | Method for improving high-temperature performance of alumina-base ceramic core |
| CN102335460A (en) * | 2011-10-15 | 2012-02-01 | 西安交通大学 | Magnesium alloy/biological ceramic bone bracket based on photocuring and gel casting and forming method of bone bracket |
| CN102887711A (en) * | 2012-08-07 | 2013-01-23 | 中国科学院长春光学精密机械与物理研究所 | Drying process of gelcasting large-sized and complex-shaped silicon carbide ceramic biscuit |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7799839B2 (en) * | 2006-10-27 | 2010-09-21 | Korea Institute Of Machinery & Materials | Porous material having hierarchical pore structure and preparation method thereof |
| CN101955353A (en) * | 2010-09-26 | 2011-01-26 | 西安交通大学 | Method for improving high-temperature performance of alumina-base ceramic core |
| CN102335460A (en) * | 2011-10-15 | 2012-02-01 | 西安交通大学 | Magnesium alloy/biological ceramic bone bracket based on photocuring and gel casting and forming method of bone bracket |
| CN102887711A (en) * | 2012-08-07 | 2013-01-23 | 中国科学院长春光学精密机械与物理研究所 | Drying process of gelcasting large-sized and complex-shaped silicon carbide ceramic biscuit |
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