CN105693276A - Silicon carbide filtering film and low temperature preparation method thereof - Google Patents
Silicon carbide filtering film and low temperature preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of porous ceramic materials and discloses a silicon carbide filtering film and a low temperature preparation method thereof. The silicon carbide filtering film comprises pure SiC, a surface film layer is prepared from fine grain silicon carbide through accumulation, has the pore diameter of 20 nanometers to 20 micrometers and film layer porosity of 40-50% and has high through porosity, low pressure drop, high strength, good thermal shock resistance and a high usage temperature. Film slurry is prepared from fine silicon carbide particles, an organosilicon precursor and a pore forming agent additive, the surface is spray-coated with the film slurry so that a film layer is formed, and the film layer is dried and sintered so that a pure silicon carbide film is obtained. The organosilicon precursor is cracked to produce a coupling phase, a sintering temperature is low, an aperture structure can be controlled easily, and the film layer can be used in an oxidation atmosphere and in a reduction atmosphere, has strong acid and base resistance and can be used for various high and low temperature fluid filtering purification such as coal gasification chemical engineering, IGCC and PFBC coal gasification generating, and high temperature flue gas, automobile exhaust and water purification.
Description
Technical field
The invention belongs to porous ceramic film material field, be specially a kind of silicon carbide filter rete and low temperature preparation method thereof。
Background technology
High-temperature ceramics filtering material generally all works when various harsh environment, usually requires that have as gas purification high-temperature ceramics filtering material: (1) high mechanical strength, high temperature resistant (300～900 DEG C) and excellent medium corrosion resistance energy；(2) Pressure Drop that high filtering accuracy is fast and low with crossing air filtration；(3) blowback, stable operation, filter efficiency height it are prone to；(4) there is good thermal stability, it is possible to bear the thermal shock that the blowback of high-voltage pulse cold air frequently causes。Meanwhile, according to its application scenario requirement, High Temperature Ceramic Filter must be able to bear the impact affecting change of component of air-flow chemical characteristic change, spray into the impact of vibration during superfine grit the efficiency of dust collection that maintenance is higher, keeps the requirements such as high flow capacity。The ceramic material selected not only has the chemistry of heat, mechanical stability, also should have ruggedness and high reliability；Especially, under high-temperature and high-pressure conditions, when there is the situation of gas phase sulfur, alkali, the corrosion of chlorine element, also require that ceramic material has high chemical stability。
The unfailing performance of the strainability of high-temperature ceramics filtering material, high high-temp stability and roadholding and long-term operation, is the key of high-temperature ceramics filtering material design。The high-temperature ceramics filtering material with filtration, desulfurization or denitration multifunctional all will be the further developing direction of gas purification material。In all kinds of ceramic filter materials, the most promising with SiC ceramic, because SiC relatively oxide ceramics has high thermal conductivity, low-expansion coefficient, thermal shock resistance are good, use the feature of temperature high (more than 1000 DEG C), the therefore preferred material in the industrial field high temperature fluid filtrations such as vehicle exhaust, Coal Chemical Industry, molten metal。
But applying maximum silicon carbide filters at present in high temperature air filtration and mostly be the oxides such as clay in conjunction with SiC ceramic, shortcoming is that thermal conductivity is low, causes that thermal shock resistance is poor so that ceramic filter material is difficult to bear big thermic load fluctuation；Particularly at high-temperature coal gasification generation technology (such as IGCC, PFBC) in, because coal contains sodium silicate, NaCl composition, the Na2Si2O5 meeting heavy corrosion oxide combined silicon carbide filtering material changed into after coal burning, cause the damage inactivation of filter, and study and show that pure SiC ceramic material is not subjected to above-mentioned corrosion, pure matter carbofrax material can use under high-temperature oxydation and reducing atmosphere simultaneously, but in pure matter silicon carbide filters development, technology is few at present, resulting product intensity is low, pore-size distribution is uneven, filter efficiency is not high, filtration pressure drop is big, pore structure is not easy to the shortcoming that blowback is cleaned, the application process of restriction silicon carbide filters。
Filtering material is in use, the filtration rete being attached to filtering material supporting body surface that filtering accuracy is played a decisive role, supporter plays intensity effect, the gradient-structure formed by the two both can ensure that requirement of strength, can ensure that again filter effect, consider filtration resistance problem, filter rete and be made general very thin, thus require that filtering rete has high toleration and high filtration performance。Existing carborundum supporter filtering material rete mostly is the oxide material such as aluminium oxide, mullite, in order to better mate with carborundum supporter, people expect to prepare pure matter silicon carbide film layer always, but due to carborundum not easy-sintering, sintering temperature high (1900～2400 DEG C), is difficult to while controlling rete pore structure and ensures again the good combination of crystal grain in rete, and silicon carbide film layer intensity prepared by conventional method is low, not resistance to erosion, the life-span is low。Therefore, use temperature various dielectric corrosions high, resistance to, intensity height, high intensity, low pressure drop, be prone to regenerate, preparation method is reliable, cost is low silicon carbide filter rete is that people are expected。
Summary of the invention
It is an object of the invention to provide a kind of silicon carbide filter rete and low temperature preparation method thereof, specifically solve as above technical problem:
One the invention solves the problems that technical problem is that: avoids existing filtering material material surface to filter rete and is mostly the material composition of the oxide ceramics such as mullite, aluminium oxide, a kind of pure matter silicon carbide filters is provided, material consists of more than 99wt% carborundum so that this kind of material can under various atmospheric conditions media-resistant corrosive power higher。
Another that the invention solves the problems that technical problem is that: avoids existing filtering material material surface to filter the weak point in rete technology of preparing, there is provided that a kind of pore structure is controlled, porosity is big, the high and low pressure drop of intensity, regenerating easily, reusable desirable pure matter silicon carbide porous filters rete。
What the invention solves the problems that another technical problem is that: adopt the low temperature preparation method being different from Conventional silicon carbide high-sintering process, it is provided that a kind of silicon carbide filter Film preparation method being suitable to large-scale production that raw material is easy to get, molding is easy, sintering temperature is low, yield rate is high, rete pore structure more easily regulates and controls。
In order to solve the technical problem existed in silicon carbide filter Film preparation, the technical solution used in the present invention is:
A kind of silicon carbide filter rete, silicon carbide filter rete consist of pure matter SiC, superficial film is piled up by fine grained carborundum and is combined into, and 20nm～20 μm, aperture, rete porosity is between 40～50%。
Described silicon carbide filter rete, in silicon carbide filter rete, pure matter SiC content is at more than 99wt%, and material is cracked carborundum by organosilane precursor and forms from sintering in conjunction with original silicon carbide silicon grain。
The preparation method of described silicon carbide filter rete, adopts thin silicon-carbide particle, organosilane precursor, pore creating material additive and organic solvent preparation rete slurry, adopts sprayed surface to prepare rete, and after drying, sintering obtains silicon carbide film layer。
The preparation method of described silicon carbide filter rete, specifically comprises the following steps that
(1) rete slurry prepares
It is (6～4) by thin silicon-carbide particle, organosilane precursor, pore creating material additive, organic solvent example by mass percentage: (5～3)): (2～1): (8～6) are blended, after mechanical agitation, ball milling obtains rete slurry；
(2) superficial film coating
Superficial film adopts spraying method to carry out, spraying method: utilize the rete pulp spraying that gas spray gun just step (1) obtains to be coated on the precast support body of rotation, thicknesses of layers is controlled by regulating relative displacement between supporter and spray gun, superficial film is obtained after drying, drying temperature is 60～80 DEG C of insulations 0.5～1.5 hour, then proceedes to be warming up to 180～220 DEG C and is incubated 1.5～2.5 hours；
(3) sintering
Filtering material supporter after coating surface rete is sintered under the protective atmosphere of vacuum, argon or other noble gas, heating rate 1～3 DEG C/min, be warming up to 600～800 DEG C, be incubated and organosilane precursor cracked substantially in 0.5～1 hour；Rear heating rate is 5～15 DEG C/min, and temperature is: 1100～1600 DEG C, is incubated 0.5～5 hour, must have silicon carbide filter rete；
(4) silicon carbide film layer (3) step obtained, in air atmosphere 750～850 DEG C of oxidation processes 0.5～1.5 hour, remove pore-forming additive so that rete porosity is promoted to design level。
The preparation method of described silicon carbide filter rete, in step (1), the granularity of thin silicon-carbide particle is between 20nm～40 μm, and organosilane precursor is polymethyl silicane；Pore-forming additive is carbon dust, and granularity is between 20nm～10 μm；Organic solvent is toluene or dimethylbenzene。
The preparation method of described silicon carbide filter rete, in step (2), spraying method: utilize gas spray gun to be coated in by pulp spraying on the precast support body of rotation, the flow velocity of spray gun rete slurry is 10～20 Grams Per Seconds, rotary speed is 5～30rpm/min, control thicknesses of layers by regulating relative displacement 50～100mm/min between supporter and spray gun, obtain superficial film after drying。
The preparation method of described silicon carbide filter rete, in step (3), by the control of spraying coating process, pure matter silicon carbide film layer THICKNESS CONTROL is between 50～1000 μm。
Present invention have the advantage that and prominent effect:
1. the silicon carbide filter rete of the present invention has single carborundum composition, ensure that material corrosion resistance under various high-temperature mediums, especially it is not suitable at oxide membranous layer filtering material under reducing atmosphere and the high-alkali corrosive environment of use, has good stability, it is ensured that the material long life。
2. the silicon carbide filter rete of the present invention has fine pore structure, it is ensured that material has good filtering accuracy and filter efficiency, and is beneficial to the realization that blowback is cleaned, and regeneration is easily, reusable。
3. the silicon carbide filter rete crystal grain combination of the present invention be secondary carborundum in conjunction with original silicon carbide silicon grain, the two is qualitative unanimously ensures that intercrystalline is firmly combined with, it is ensured that material has high intensity and thermal shock resistance。
4. the silicon carbide filter Film preparation method technique sintering temperature of the present invention is well below Conventional silicon carbide sintering temperature, and pore structure is prone to precise controlling, and preparation cost is low, can designing the product of different size as required, with short production cycle, cost is low, it is easily achieved, it is possible to ensure properties of product。
5. silicon carbide filter film material application provided by the invention is wide, under the atmosphere such as oxidation, reduction, high chlorine, alkali, sulfur, silicon can long time use, more can use under the high temperature of 1000 DEG C, can be used for the various industrial smokes such as Coal Chemical Industry and high-temperature coal gasification generation technology raw gas filtration, high-temperature boiler, can be additionally used in sewage water filtration process。
In a word, this kind of silicon carbide filter film layer group becomes pure matter carborundum, is absent from oxide etc. in conjunction with phase, has high pass porosity, low pressure drop, intensity is high, thermal shock resistance is good, use the feature that temperature is high, and preparation method is easily achieved, it is possible to ensure properties of product。
Accompanying drawing explanation
Fig. 1: silicon carbide filter film surface shape appearance figure。
Fig. 2: silicon carbide filter film surface enlarged drawing。
Fig. 3: silicon carbide filter rete port shape appearance figure。
Fig. 4: silicon carbide filter rete and supporter interface cohesion figure。
Detailed description of the invention
In a specific embodiment, the silicon carbide filter rete of the present invention and low temperature preparation method thereof, superficial film raw material components is (according to the mass fraction):
| Thin silicon-carbide particle (20nm～40 μm) | 6～4 |
| Organosilane precursor (polymethyl silicane) | 5～3 |
| Pore creating material additive (carbon dust, 20nm～10 μm) | 2～1 |
| Organic solvent (toluene or dimethylbenzene) | 8～6 |
In the constitutive material of silicon carbide filter rete, organosilane precursor cracks in sintering process and is transformed into carborundum and small amounts silicon, original silicon carbide silicon grain is combined by the carborundum generated, provide intensity for rete to ensure, and wherein a small amount of silicon oxide and carbon dust in raw material react formation carborundum, it is to avoid the existence of impurity phase, then remove pore-forming additive in the follow-up oxidizing process, be remarkably improved rete porosity so that material consist of carborundum。Pure matter silicon carbide film layer is for improving the strength of materials, heat shock resistance, high-temperature stability and playing an important role creep rupture life。
In prepared by material, different raw materials forms, granularity selection, it is ensured that silicon carbide filter rete has high pass porosity and rational pore structure, it is ensured that material permeability is good, there is low filter pressure, the guarantee filtering accuracy that simultaneously fine rete design can be good。
The preparation method of the pure matter silicon carbide filter rete of the present invention, adopt thin silicon-carbide particle, organosilane precursor, pore creating material additive, organic solvent preparation rete raw material, spin coating process is adopted to filter rete in the preparation of filtering material supporting body surface, after drying, sintering and oxidation removal pore creating material, obtain pure matter silicon carbide filter rete, mainly comprise the steps that
(1) rete slurry prepares
It it is (6～4) by thin silicon-carbide particle, organosilane precursor, pore creating material additive, organic solvent example by mass percentage: (5～3): (2～1): (8～6) blending and stirring, rete slurry is obtained through ball milling, Ball-milling Time is 1～2 hour, stand-by。
Carborundum granularity is between 20nm～40 μm, and pore-forming additive (carbon dust) is between 20nm～10 μm, and organosilane precursor selects polymethyl silicane；Organic solvent is toluene or dimethylbenzene。
(2) superficial film coating preparation
Superficial film adopts spin coating process to carry out, spraying method: utilize the rete pulp spraying that gas spray gun just step (1) obtains to be coated on the filtering material supporter of rotation, the flow velocity of spray gun rete slurry is 10～20 Grams Per Seconds, rotary speed is 5～30rpm/min, control thicknesses of layers by regulating relative displacement (50～100mm/min) between supporter and spray gun, obtain superficial film after drying。By dried membrane tube outside diameter measuring, control table face mask layer thickness is between 50～1000 μm。
(3) sintering
Rete was through 60～80 DEG C, 0.5～1.5 hour; after then proceeding to be warming up to 180～220 DEG C, 1.5～2.5 hours dried; filtering material supporter after coating surface rete is sintered under the protective atmosphere of vacuum, argon or other noble gas: initial heating rate 1～3 DEG C/min; it is warming up to 600～800 DEG C, is incubated and organosilane precursor was cracked substantially in 0.5～1 hour；Then proceeding to heat up, heating rate is 5～15 DEG C/min, and temperature is 1100～1600 DEG C, is incubated 0.5～5 hour, must have silicon carbide filter rete。Wherein,
Rete is through the dried of two benches different temperatures, and its feature and effect be: low-temperature zone makes organic solvent slowly volatilize, and so as to remove, can avoid, owing to organic solvent evaporation acutely bubble occurs in inside, producing hole；High temperature section is the organosilane precursor cure treatment stage, can avoid the generation of organosilane precursor temperature flowing phenomenon very well, it is ensured that organosilane precursor is evenly distributed。
Rete adopts the sintering processes of two benches different temperatures, and its feature and effect be: low-temperature region is organosilane precursor cleavage stages, and rate of cleavage is too fast, easily a large amount of venting, rete is ftractureed, adopts the control heating rate that slow heating rate can be good, it is to avoid the generation of defect；Organosilane precursor, after slowly cracking, is entering carborundum grain and is breeding the stage of growing up, and programming rate can be accelerated, and can improve preparation efficiency。
(4) by silicon carbide filter rete, 750～850 DEG C of oxidation processes 0.5～1.5 hour in air atmosphere, remove pore-forming additive so that rete porosity is promoted to design level。
In the present invention, the average pore size of silicon carbide filter rete is between 20nm～20 μm, and porosity is between 40～50%。In described pure matter silicon carbide filter rete, pure matter SiC content is at more than 99wt%, and surplus is impurity element, and material internal crystal grain combines and is combined into by silicon-carbide particle completely, is absent from clay or other oxides in conjunction with phase。
Below, described in further detail by the embodiment present invention。
Embodiment 1
Being that 4:5:2:8 is blended by 20nm silicon-carbide particle, polymethyl silicane, 20nm carbon dust, dimethylbenzene example in mass ratio, after mechanical agitation, ball milling obtains rete slurry in 1.5 hours。
Utilize gas spray gun to be coated in by pulp spraying on the filtering material supporter of rotation, control thicknesses of layers by regulating relative displacement between supporter and spray gun, obtain superficial film after drying。Spray gun material flow is 10 Grams Per Seconds, filters a stay tube rotating speed 10rpm/ minute。Supporter and spray gun relative displacement are 70mm/min, after spraying, rete was through 70 DEG C, 1 hour, then proceed to be warming up to 200 DEG C, 2 hours dried, dried rete is sintered under vacuo, initial heating rate 1 DEG C/min, is warming up to 600 DEG C, is incubated and organosilane precursor was cracked substantially in 0.5 hour；Then proceeding to heat up, heating rate is 5 DEG C/min, and temperature is 1100 DEG C, is incubated 2 hours, must have silicon carbide filter rete。
Again by above-mentioned silicon carbide filter rete 800 DEG C of oxidation processes 1 hour in air atmosphere, remove pore-forming additive so that rete porosity is promoted to design level。
Thus, obtaining silicon carbide filter thicknesses of layers is 400 μm, and average pore size is 20nm, and porosity is 45%, rete heatproof 1000 DEG C。
Embodiment 2
Being that 5:3:1:6 is blended by 40 μm of silicon-carbide particles, polymethyl silicane, 20 μm of carbon dust, toluene examples in mass ratio, after mechanical agitation, ball milling obtains rete slurry in 1 hour。
Utilize gas spray gun to be coated in by pulp spraying on the filtering material supporter of rotation, control thicknesses of layers by regulating relative displacement between supporter and spray gun, obtain superficial film after drying。Spray gun material flow is 20 Grams Per Seconds, filters a stay tube rotating speed 30rpm/ minute。Supporter and spray gun relative displacement are 50mm/min, after spraying, rete was through 70 DEG C, 1 hour, then proceed to be warming up to 200 DEG C, 2 hours dried, dried rete is sintered under vacuo, initial heating rate 3 DEG C/min, is warming up to 800 DEG C, is incubated and organosilane precursor was cracked substantially in 1 hour；Then proceeding to heat up, heating rate is 10 DEG C/min, and temperature is 1400 DEG C, is incubated 2 hours, obtains silicon carbide filter rete。
Again by above-mentioned silicon carbide filter rete 800 DEG C of oxidation processes 1 hour in air atmosphere, remove pore-forming additive so that rete porosity is promoted to design level。
Thus, obtaining silicon carbide filter thicknesses of layers 1000 μm, average pore size 20 μm, porosity is 42%, rete heatproof 1000 DEG C。
Embodiment 3
Being that 5.5:4:2:7 is blended by 10 μm of silicon-carbide particles, polymethyl silicane, 500nm carbon dust, toluene example in mass ratio, after mechanical agitation, ball milling obtains rete slurry in 1 hour。
Utilize gas spray gun to be coated in by pulp spraying on the filtering material supporter of rotation, control thicknesses of layers by regulating relative displacement between supporter and spray gun, obtain superficial film after drying。Spray gun material flow is 10 Grams Per Seconds, filters a stay tube rotating speed 10rpm/ minute。Supporter and spray gun relative displacement are 5mm/min, after spraying, rete was through 70 DEG C, 1 hour, then proceed to be warming up to 200 DEG C, 2 hours dried, dried rete is sintered under vacuo, initial heating rate 2 DEG C/min, is warming up to 800 DEG C, is incubated and organosilane precursor was cracked substantially in 0.5 hour；Then proceeding to heat up, heating rate is 15 DEG C/min, and temperature is 1600 DEG C, is incubated 5 hours, obtains silicon carbide filter rete。
Again by above-mentioned silicon carbide filter rete 800 DEG C of oxidation processes 1 hour in air atmosphere, remove pore-forming additive so that rete porosity is promoted to design level。
Thus, obtaining silicon carbide filter thicknesses of layers 1000 μm, average pore size 500nm, porosity is 50%, rete heatproof 1000 DEG C。
As it is shown in figure 1, from film surface pattern it can be seen that the present invention prepares the face flatness height of rete, there is uniform pore structure。
As in figure 2 it is shown, amplify it can be seen that rete inner pore is evenly distributed from film surface, aperture uniform level is high, it is ensured that rete has higher filtering accuracy。
As it is shown on figure 3, from rete port pattern it can be seen that the carborundum cladding that the internal original silicon carbide silicon grain of rete is generated by organosilane precursor cracking combines, it is ensured that rete has higher intensity。
As shown in Figure 4, from rete and supporter interface it can be seen that rete is firm with supporter interface cohesion, rete difficult drop-off, it can be ensured that rete service life。
Embodiment result shows, the invention provides a kind of silicon carbide filter rete and low temperature preparation method thereof, this kind of silicon carbide filter film layer group becomes 99% carborundum, it is absent from oxide etc. in conjunction with phase, have high pass porosity, low pressure drop, intensity is high, thermal shock resistance is good, use the feature that temperature is high, preparation method is easily achieved, it is possible to ensure properties of product。The present invention adopts organosilane precursor (polymethyl silicane Polymethylsilane, PMS) cracking generation is in conjunction with phase, sintering temperature is low, pore structure controls easily, prepared rete can use under oxidizing atmosphere, can also using under reducing atmosphere, acid and alkali resistance corrosive nature is strong, can be used for the various high and low temperature filtering flows such as coal gasification chemical industry and IGCC, PFBC coal gasification power generation, high-temperature flue gas, vehicle exhaust, Water warfare and purifies。
Claims (7)
1. a silicon carbide filter rete, it is characterised in that: silicon carbide filter rete consist of pure matter SiC, superficial film by fine grained carborundum pile up be combined into, 20nm～20 μm, aperture, rete porosity is between 40～50%。
2. the silicon carbide filter rete described in claim 1, it is characterised in that: in silicon carbide filter rete, pure matter SiC content is at more than 99wt%, and material is cracked carborundum by organosilane precursor and forms from sintering in conjunction with original silicon carbide silicon grain。
3. the preparation method of the silicon carbide filter rete described in a claim 1, it is characterized in that: adopt thin silicon-carbide particle, organosilane precursor, pore creating material additive and organic solvent preparation rete slurry, adopting sprayed surface to prepare rete, after drying, sintering obtains silicon carbide film layer。
4. the preparation method of the silicon carbide filter rete described in claim 3, it is characterised in that specifically comprise the following steps that
(1) rete slurry prepares
It is (6～4) by thin silicon-carbide particle, organosilane precursor, pore creating material additive, organic solvent example by mass percentage: (5～3)): (2～1): (8～6) are blended, after mechanical agitation, ball milling obtains rete slurry；
(2) superficial film coating
Superficial film adopts spraying method to carry out, spraying method: utilize the rete pulp spraying that gas spray gun just step (1) obtains to be coated on the precast support body of rotation, thicknesses of layers is controlled by regulating relative displacement between supporter and spray gun, superficial film is obtained after drying, drying temperature is 60～80 DEG C of insulations 0.5～1.5 hour, then proceedes to be warming up to 180～220 DEG C and is incubated 1.5～2.5 hours；
(3) sintering
Filtering material supporter after coating surface rete is sintered under the protective atmosphere of vacuum, argon or other noble gas, heating rate 1～3 DEG C/min, be warming up to 600～800 DEG C, be incubated and organosilane precursor cracked substantially in 0.5～1 hour；Rear heating rate is 5～15 DEG C/min, and temperature is: 1100～1600 DEG C, is incubated 0.5～5 hour, must have silicon carbide filter rete；
(4) silicon carbide film layer (3) step obtained, in air atmosphere 750～850 DEG C of oxidation processes 0.5～1.5 hour, remove pore-forming additive so that rete porosity is promoted to design level。
5. the preparation method of the silicon carbide filter rete described in claim 4, it is characterised in that in step (1), the granularity of thin silicon-carbide particle is between 20nm～40 μm, and organosilane precursor is polymethyl silicane；Pore-forming additive is carbon dust, and granularity is between 20nm～10 μm；Organic solvent is toluene or dimethylbenzene。
6. the preparation method of the silicon carbide filter rete described in claim 4, it is characterized in that, in step (2), spraying method: utilize gas spray gun to be coated in by pulp spraying on the precast support body of rotation, the flow velocity of spray gun rete slurry is 10～20 Grams Per Seconds, rotary speed is 5～30rpm/min, controls thicknesses of layers by regulating relative displacement 50～100mm/min between supporter and spray gun, obtains superficial film after drying。
7. the preparation method of the silicon carbide filter rete described in claim 4, it is characterised in that in step (3), by the control of spraying coating process, pure matter silicon carbide film layer THICKNESS CONTROL is between 50～1000 μm。
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| CN108176249B (en) * | 2017-12-28 | 2021-03-30 | 南京工业大学 | Preparation method of silicon carbide nanofiber membrane |
| CN109678522A (en) * | 2018-12-20 | 2019-04-26 | 中国科学院上海硅酸盐研究所 | A kind of normal pressure solid-phase sintered silicon carbide film support and preparation method thereof |
| CN111470869A (en) * | 2020-05-08 | 2020-07-31 | 武汉工程大学 | Preparation method of separation membrane based on high-solid-content silicon carbide slurry |
| CN111470869B (en) * | 2020-05-08 | 2022-07-19 | 武汉工程大学 | Preparation method of separation membrane based on high-solid-content silicon carbide slurry |
| CN111960846A (en) * | 2020-07-17 | 2020-11-20 | 浙江吉成新材股份有限公司 | Nano porous material and preparation method thereof |
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