CN118255592A - Two-step co-firing preparation method of silicon carbide ceramic support and film - Google Patents
Two-step co-firing preparation method of silicon carbide ceramic support and film Download PDFInfo
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- CN118255592A CN118255592A CN202410432083.5A CN202410432083A CN118255592A CN 118255592 A CN118255592 A CN 118255592A CN 202410432083 A CN202410432083 A CN 202410432083A CN 118255592 A CN118255592 A CN 118255592A
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 52
- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000010344 co-firing Methods 0.000 title claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000007547 defect Effects 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 229920000193 polymethacrylate Polymers 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 21
- 238000005507 spraying Methods 0.000 abstract description 14
- 238000004321 preservation Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000001471 micro-filtration Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- -1 al 2O3 Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
Abstract
The invention discloses a two-step co-firing preparation method of a silicon carbide ceramic support and a film layer. Firstly, a small-particle-size silicon carbide film layer is coated on the surface of a silicon carbide support green body, and the film thickness is controlled and the film defect is reduced by regulating and controlling the spraying time and the spraying distance. And then, adopting a two-step sintering process to perform one-time co-sintering of the membrane layer and the support body, so as to prepare the silicon carbide ceramic microfiltration membrane with excellent performance. Compared with the step-by-step sintering method, the method shortens half of heat preservation time, greatly reduces the preparation energy consumption of the silicon carbide film, and provides a new way for low-cost preparation of the ceramic film.
Description
Technical Field
The invention belongs to the technical field of porous ceramic membrane material preparation, and relates to a two-step co-firing preparation method of a silicon carbide ceramic support and a membrane layer.
Background
SiC films are novel inorganic film materials that have excellent mechanical strength, chemical stability, thermal shock resistance, and hydrophilicity, and have been increasingly being accepted in academia and industry in recent years. SiC membranes have a higher efficiency in oil-water emulsion separation than polymers (e.g., PVDF) and inorganic materials (e.g., al 2O3、ZrO2). However, most commercial SiC ceramic films are prepared by high temperature (> 2000 ℃) recrystallization processes in an inert atmosphere, and their wide use is hampered by high manufacturing costs. Therefore, reducing sintering energy consumption is an important issue in the current ceramic film field.
In order to reduce the preparation cost of the inorganic ceramic film, besides adopting a method of adding a sintering aid to reduce the temperature, the co-firing process is the most promising technology for reducing the cost, so that the preparation cost can be reduced, and the preparation period can be shortened. However, there are still many difficulties in the co-firing process of the film layer and the support layer with larger particle size difference, and the thermal expansion rate, the sintering shrinkage rate and the difference between the sintering procedures of the film layer and the support body are considered. In the cofiring process, the sintering temperature of the applicable film layer is difficult to reach the sintering temperature required by the support body, so that the bending resistance of the support body is too low; the sintering temperature of the applicable support body can cause excessive sintering of the film layer, and the film layer and the support body are not matched to generate defects such as cracking.
For example, chinese patent No. CN117820007a reports an ultra-low temperature co-firing preparation method of high flux silicon carbide ceramic membranes. By adding the alkaline liquid phase sintering auxiliary agent, the sintering temperature can be reduced, the rheological property of the film-making liquid can be regulated, and the asymmetric silicon carbide ceramic film with high pure water permeability can be prepared at a low temperature of 600 ℃, so that the thermal stress difference between the film layer and the supporting layer is avoided, and the problem of mismatching of the temperature of the film layer and the supporting layer is avoided. Chinese patent No. 108911706A reports a co-firing preparation method of a fly ash ceramic microfiltration membrane, wherein rigid fibers are doped in a fly ash support to relieve the matching problem in the sintering process of the support and a membrane layer, and the microfiltration membrane with the pore diameter of about 100 nm and the membrane thickness of 40-50 mu m is prepared by heat preservation at 1050 ℃ of 2 h. Chinese patent CN115572178a reports a method for preparing a silicon carbide support and a film by co-firing. The defect-free film layer is prepared by adjusting the factors such as the particle size, sintering temperature, sintering atmosphere and the like of the support body and the film layer silicon carbide, so that one-step sintering of the support body and the film layer is realized, and a large amount of energy consumption is saved. It can be seen that in order to realize co-firing preparation of the support and the film, the existing solutions are to control the formulation of the support so as to reduce the sintering temperature of the support or slow down the shrinkage of the support.
Disclosure of Invention
The invention aims to reduce the energy consumption for preparing the asymmetric ceramic membrane and provides a new way for preparing the ceramic membrane at low cost. The invention provides the optimal sintering temperature of the support body and the membrane layer, and the optimal preparation of the asymmetric pure silicon carbide membrane is realized by carrying out sectional treatment on the heat preservation process through the optimal sintering process and reducing the shrinkage of the membrane layer on the basis of meeting the strength application of the support body.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
(1) Uniformly mixing silicon carbide powder and NaA molecular sieve sintering aid powder according to a mass ratio, adding a certain proportion of polyvinyl alcohol (PVA) and water, uniformly mixing, pressing at 8 MPa to prepare silicon carbide sheet-shaped (phi 30 mm multiplied by 3 mm) and strip-shaped (50 mm multiplied by 6 mm multiplied by 6 mm) green bodies, and drying and forming;
(2) Dispersing silicon carbide powder in a solution containing ammonium polymethacrylate and methylcellulose, fully stirring, regulating the pH value of a coating solution to be 9-10 by dropwise adding ammonia water, then dropwise adding an antifoaming agent TL-56NQ, stirring at a low speed for 20 min, and carrying out vacuum defoaming on the solution before coating to prevent film defects caused by excessive bubbles in the solution;
(3) Coating the coating liquid obtained in the step (2) on the surface of a silicon carbide support green body, and placing the prepared pure silicon carbide asymmetric green body film in an oven for drying;
(4) And placing the asymmetric green body film in a muffle furnace for sintering, performing two-step sintering, and finally cooling to room temperature along with the furnace to obtain the prepared silicon carbide ceramic film.
In the step (1), after the sintering aid and the silicon carbide powder are mixed, the proportion of the sintering aid to the total mass is 5-20 wt%, and the addition amount of PVA is about 5-10 wt%.
In the step (2), the solid content of the film forming liquid is 2-10wt% and the methyl cellulose content is 0.5-2wt% of the solid content.
And (3) drying the silicon carbide green film prepared in the step (3) in a baking oven at 40-80 ℃ for 8-24 hours.
The sintering procedure in the step (4) is a two-step heat preservation procedure with high temperature firstly and then low temperature, the high temperature adopts the optimal sintering temperature (1000-1100 ℃) of the support body, the low temperature adopts the optimal sintering temperature (900-1000 ℃) of the film layer, the co-sintering procedure is to control the high temperature heat preservation time to be (0.5-1 h), the low temperature heat preservation time to be (1-4 h), the heating rate to be controlled to be 1-2 ℃ per minute, and the sintering atmosphere is air.
The asymmetric silicon carbide ceramic membrane prepared by the invention has a separation layer film thickness of about 10-30 mu m and an average pore diameter of 0.1-0.3 mu m.
Compared with the prior art, the invention has the beneficial effects that:
1. According to the invention, on the basis of the sintering temperature of the film layer and the supporting layer, the one-step sintering of the silicon carbide supporting body and the film layer is realized by using a two-step co-sintering method, and the preparation method greatly reduces the preparation working procedures and the sintering energy consumption, thereby providing a new way for preparing the inorganic ceramic film such as silicon carbide and the like at low cost.
2. By adopting the two-step co-firing method, the strength of the support body can meet the requirement and the excessive sintering of the film layer can be avoided by the short-time high-temperature calcination.
Drawings
FIG. 1 is a surface SEM image of an asymmetric silicon carbide ceramic membrane prepared according to example 1.
FIG. 2 is a graph showing pore size distribution of an asymmetric silicon carbide ceramic membrane prepared in example 1.
FIG. 3 is an oil-in-water emulsion separation performance of the asymmetric silicon carbide ceramic membrane prepared in example 1.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific examples, which are given for illustration only and are not intended to limit the scope of the invention.
Example 1
A two-step co-firing preparation method of a silicon carbide ceramic support and a film layer comprises the following specific steps:
(1) Firstly, silicon carbide powder with average particle sizes of 5 mu m and 3.9 mu m and NaA molecular sieve powder are adopted according to 84:16, and adding a binder PVA, wherein the amount of PVA is 5% of the total mass.
(2) Fully grinding the powder, weighing 2.5g of the powder which is uniformly mixed, pressing the mixed powder into a sheet-shaped and strip-shaped green body by a tablet press under the condition of 8 MPa, and drying 12h at normal temperature.
(3) Preparing silicon carbide particle coating liquid with the solid content of 10 wt percent. Firstly, dispersing agent ammonium polymethacrylate (1 wt% of silicon carbide solid content) is weighed and dispersed in deionized water, then 10 wt% silicon carbide powder is added, 2 wt% MC solution is added, and the mixture is fully stirred for 6h at 400 r/min. And dropwise adding an antifoaming agent TL-56NQ before spraying, and stirring at a low speed for 30 min.
(4) The green sheet type support is coated with a film layer by a spraying method, the spraying time is 5 s times, the green sheet type support is placed in a 60 ℃ oven for drying and then is sprayed, the total spraying time is 25 s, and the green sheet type support is sintered after the oven is dried. Under the air atmosphere, the temperature is increased from 200 ℃ to 500 ℃ at 2 ℃ per minute, then the temperature is increased to 1050 ℃ at 1 ℃ per minute, the temperature is kept at 1h, the cooling rate is set to be 1 ℃ per minute according to the natural cooling rate of the muffle furnace, the temperature is reduced to 900 ℃ and kept at 1h, and finally the furnace is cooled to room temperature.
The microstructure of the surface was observed by scanning electron microscopy, and as can be seen in fig. 1, the silicon carbide surface was defect free and exhibited a porous structure with distinct sintered necks between particles. And (3) performing bending strength test on the porous silicon carbide ceramic support body by adopting a fine ceramic three-point bending method, wherein the result shows that the strength is 21.7-MPa. The average pore diameter of the asymmetric silicon carbide ceramic membrane is about 0.22 mu m (as shown in fig. 2), the membrane thickness is about 21 mu m, the pure water permeability is about 1920L m -1·h-1·bar-1, the retention rate of 100 ppm oil-in-water emulsion under the conditions of 0.5 bar and 0.5 m/s reaches 94.3%, and the oil content of the filtered permeate is only 5.7 mg L -1, so that the national emission standard is met. As can be seen from fig. 3, after the filtration of the silicon carbide film, the permeate is clear and transparent, and almost no oil drop exists, which proves that the silicon carbide film has excellent oil-water separation performance.
Example 2
A two-step co-firing preparation method of a silicon carbide ceramic support and a film layer comprises the following specific steps:
(1) Firstly, silicon carbide powder with average particle sizes of 5 mu m and 3.9 mu m and NaA molecular sieve powder are adopted according to 84:16, and adding a binder PVA, wherein the amount of PVA is 5% of the total mass.
(2) Fully grinding the powder, weighing 2.5g of the powder which is uniformly mixed, pressing the mixed powder into a sheet-shaped and strip-shaped green body by a tablet press under the condition of 8 MPa, and drying 12h at normal temperature.
(3) Preparing silicon carbide particle coating liquid with the solid content of 10 wt percent. Firstly, dispersing agent ammonium polymethacrylate (1 wt% of silicon carbide solid content) is weighed and dispersed in deionized water, then 10 wt% silicon carbide powder is added, 2 wt% MC solution is added, and the mixture is fully stirred for 6h at 400 r/min. And dropwise adding an antifoaming agent TL-56NQ before spraying, and stirring at a low speed for 30 min.
(4) The green sheet type support is coated with a film layer by a spraying method, the spraying time is 5 s times, the green sheet type support is placed in a 60 ℃ oven for drying and then is sprayed, the total spraying time is 25 s, and the green sheet type support is sintered after the oven is dried. Under the air atmosphere, the temperature is increased from 200 ℃ to 500 ℃ at 2 ℃ per minute, then the temperature is increased to 1050 ℃ at 1 ℃ per minute, the temperature is kept at 1 h, the cooling rate is set to be 1 ℃ per minute according to the natural cooling rate of the muffle furnace, the temperature is reduced to 900 ℃ and kept at 0.5: 0.5 h, and finally the furnace is cooled to room temperature.
And (3) carrying out bending strength test on the porous silicon carbide ceramic support body by adopting a fine ceramic three-point bending method, wherein the result shows that the strength is 17.2 MPa. The film thickness of the asymmetric silicon carbide ceramic film is about 21 mu m, and the pure water permeability is about 1650L m -1·h-1·bar-1.
Example 3
A two-step co-firing preparation method of a silicon carbide ceramic support and a film layer comprises the following specific steps:
(1) Firstly, silicon carbide powder with average particle sizes of 5 mu m and 3.9 mu m and NaA molecular sieve powder are adopted according to 84:16, and adding a binder PVA, wherein the amount of PVA is 5% of the total mass.
(2) Fully grinding the powder, weighing 2.5g of the powder which is uniformly mixed, pressing the mixed powder into a sheet-shaped and strip-shaped green body by a tablet press under the condition of 8 MPa, and drying 12h at normal temperature.
(3) Preparing silicon carbide particle coating liquid with the solid content of 10 wt percent. Firstly, dispersing agent ammonium polymethacrylate (1 wt% of silicon carbide solid content) is weighed and dispersed in deionized water, then 10 wt% silicon carbide powder is added, 2 wt% MC solution is added, and the mixture is fully stirred for 6h at 400 r/min. And dropwise adding an antifoaming agent TL-56NQ before spraying, and stirring at a low speed for 30 min.
(4) The green sheet type support is coated with a film layer by a spraying method, the spraying time is 5 s times, the green sheet type support is placed in a 60 ℃ oven for drying and then is sprayed, the total spraying time is 25 s, and the green sheet type support is sintered after the oven is dried. Under the air atmosphere, the temperature is increased from 200 ℃ to 500 ℃ at 2 ℃ per minute, then the temperature is increased to 1050 ℃ at 1 ℃ per minute, the temperature is kept at 0.5 h, the cooling rate is set to be 1 ℃ per minute according to the natural cooling rate of the muffle furnace, the temperature is reduced to 900 ℃ and kept at 2h, and finally the furnace is cooled to room temperature.
And (3) performing bending strength test on the porous silicon carbide ceramic support body by adopting a fine ceramic three-point bending method, wherein the result shows that the strength is 15.0 MPa. The film thickness of the asymmetric silicon carbide ceramic film is about 21 mu m, and the pure water permeability is about 2200L m -1·h-1·bar-1.
Claims (5)
1. A two-step co-firing preparation method of a silicon carbide ceramic support and a film layer is characterized by comprising the following specific steps:
(1) Uniformly mixing silicon carbide powder and NaA molecular sieve sintering aid powder according to a certain proportion, adding polyvinyl alcohol (PVA) and water according to a certain proportion, uniformly mixing, pressing into silicon carbide sheet-shaped or strip-shaped green bodies under the condition of 8MPa, and drying and forming;
(2) Dispersing silicon carbide powder in a solution containing ammonium polymethacrylate and methylcellulose, fully stirring, regulating the pH value of a coating solution to be 9-10 by dropwise adding ammonia water, then dropwise adding an antifoaming agent TL-56NQ, stirring at a low speed for 20 min, and carrying out vacuum defoaming on the solution before coating to prevent film defects caused by excessive bubbles in the solution;
(3) Coating the coating liquid obtained in the step (2) on the surface of the silicon carbide support green body prepared in the step (1), and placing the prepared silicon carbide asymmetric green body film in an oven for drying;
(4) And placing the asymmetric green body film in a muffle furnace for sintering, preparing the asymmetric green body film by a two-step co-sintering process, and finally cooling the asymmetric green body film to room temperature along with the furnace to obtain the prepared asymmetric pure silicon carbide ceramic film.
2. The two-step co-firing preparation method of the silicon carbide ceramic support and the film layer according to claim 1, wherein the proportion of the sintering aid after the sintering aid and the silicon carbide powder in the step (1) are mixed is 5-20wt% and the addition amount of PVA is about 5-10wt% of the total mass.
3. The method for preparing the silicon carbide ceramic support and the film layer by two-step co-firing according to claim 1, wherein the solid content of the film preparation liquid in the step (2) is 2-10 wt%, and the methyl cellulose content is 0.5-2 wt% of the solid content.
4. The method for preparing the silicon carbide ceramic support and the film layer by two-step co-firing according to claim 1, wherein the silicon carbide green film prepared in the step (3) is dried in an oven at 40-80 ℃ for 8-24 hours.
5. The method for preparing the silicon carbide ceramic support and the film layer by two-step co-firing according to claim 1, wherein the sintering procedure in the step (4) is to raise the temperature from room temperature to 200 ℃ at 1-2 ℃ per minute, raise the temperature from 200 ℃ to 500 ℃ at 1-2 ℃ per minute, raise the temperature to 1050 ℃ at 1-2 ℃ per minute and keep the temperature at 0.5-1 h, set the cooling rate to 1 ℃ per minute according to the natural cooling rate of the muffle furnace, lower the temperature to 900 ℃ and keep the temperature at 0.5-2 h, and finally cool the ceramic support and the film layer to room temperature along with the furnace.
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| Publication Number | Publication Date |
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| CN118255592A true CN118255592A (en) | 2024-06-28 |
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