CN113999046B - Preparation method of low-temperature reaction sintered silicon carbide ceramic membrane - Google Patents
Preparation method of low-temperature reaction sintered silicon carbide ceramic membrane Download PDFInfo
- Publication number
- CN113999046B CN113999046B CN202111458282.6A CN202111458282A CN113999046B CN 113999046 B CN113999046 B CN 113999046B CN 202111458282 A CN202111458282 A CN 202111458282A CN 113999046 B CN113999046 B CN 113999046B
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- temperature
- heating
- sintering
- biscuit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a preparation method of a low-temperature reaction sintered silicon carbide ceramic membrane. The silicon carbide ceramic membrane is prepared from raw materials such as silicon carbide powder, silicon powder, carbon black, naCl-KCl fused salt, kaolin, sodium carboxymethylcellulose, PVP, glycerol, water and the like through the processes of batching, mixing, forming, drying, sintering, soaking in water and desalting. The invention bonds SiC raw material particles into a continuous porous ceramic support body through a beta-SiC new phase generated by silicon and carbon solid phase reaction and a molten salt liquid phase reaction, nano pores constructed by interweaving SiC nano fibers are formed on the surface, the volume density is small, and the invention has the characteristics of low sintering temperature, low oxide content, high internal porosity, nano pores on the surface, acid and alkali resistance and the like.
Description
Technical Field
The invention belongs to a preparation method of a porous ceramic material in the technical field of inorganic membrane separation materials, and particularly relates to a preparation method of a low-temperature reaction sintered silicon carbide ceramic membrane.
Background
The ceramic membrane separation technology is an efficient and energy-saving separation technology, and the application field of the ceramic membrane separation technology relates to the industries of chemical industry, petroleum and petrochemical industry, biochemical industry, food, electronics, medicine and the like. Ceramic membranes on the market mainly comprise materials such as alumina, titania, silica, zirconia, silicon carbide and the like. Among them, silicon carbide ceramic membranes are receiving a high attention due to their excellent properties, and in particular, their application in the field of water treatment is rapidly developing. The silicon carbide ceramic film mainly comprises a silicon carbide ceramic support body, a silicon carbide transition layer and a silicon carbide film layer.
At present, the preparation of SiC ceramic support bodies mainly comprises liquid phase sintering, reaction sintering, pressureless sintering, recrystallization sintering and the like. The pressureless sintering and recrystallization sintering of the silicon carbide ceramic membrane have high temperature, high energy consumption, high requirements on sintering furnace equipment and high cost; the liquid phase sintering usually adopts an oxide with a low melting point as a sintering aid, the sintering temperature is low, but the oxide content is high; the reaction sintering temperature is relatively low, but the ceramic membrane has poor quality and relatively high cost. Each process has advantages and disadvantages. The patent 'a preparation method of a low-temperature sintered acid and alkali resistant porous silicon carbide ceramic support body (application number: CN 201710656733.4)' utilizes an acid and alkali resistant sintering aid to prepare the acid and alkali resistant porous silicon carbide ceramic support body with high firing mechanical strength, high porosity and acid and alkali resistance below 1400 ℃. In the patent of the liquid phase sintering multi-channel silicon carbide ceramic membrane and the preparation method thereof (application number: CN 201810075180.8), kaolin and talc are contained in raw materials of the support body, and the sintering temperature is effectively reduced by liquid phase sintering and is below 1500 ℃. The preparation method of the multi-channel silicon carbide ceramic membrane (application number: CN 201810075202.0) comprises the steps of mixing different silicon carbide powder I, silicon carbide powder II and the pore-forming agent mixture to obtain a pug, carrying out extrusion molding to obtain a biscuit, drying and then firing to obtain the multi-channel silicon carbide ceramic membrane. In the patent of "a silicon carbide ceramic membrane and a preparation method thereof (application No. CN 201510449442.9)", siC aggregate, sintering aid, toughening aid and polymer binder are mixed according to a certain proportion, and the porous silicon carbide ceramic membrane is obtained after stirring, ball milling, molding, high-temperature sintering, film coating and sintering. In the patent 'a normal-pressure solid-phase sintered silicon carbide film support and a preparation method thereof (application number: CN 201811564686.1)', one of submicron-grade silicon carbide powder or nanoscale silicon carbide powder, micron-grade silicon carbide powder, carbon powder, a sintering aid and an organic binder are mixed to obtain mixed powder, and a plasticizer, a lubricant and water are added into the mixed powder for mixing to obtain water-based silicon carbide cement; and extruding and molding the obtained water-based silicon carbide slurry, drying, and heating to 1750-2200 ℃ for sintering to obtain the silicon carbide film support body. In the patent 'a high-temperature-resistant corrosion-resistant reaction-sintered silicon carbide film support and a preparation method thereof (application number: CN 201911039324.5)', submicron or micron silicon carbide powder, submicron or micron silicon nitride powder and a carbon precursor are fully mixed to obtain mixed powder; molding to obtain a green body; and sintering the green body to obtain the high-temperature-resistant corrosion-resistant reaction-sintered silicon carbide film support.
The method has the advantages of high equipment requirement for sintering the silicon carbide ceramic support body at high temperature (above 1700 ℃), high energy consumption and high cost. The silicon carbide ceramic support body sintered at low temperature (about 1500 ℃) often adopts low-melting-point oxide sintering aids and the like, and has the problems of poor acid and alkali resistance, low strength and the like.
Disclosure of Invention
In order to solve the problems in the background technology, the invention provides a preparation method of a low-temperature reaction sintered silicon carbide ceramic membrane, which is characterized in that a SiC new phase generated by the solid-phase reaction of silicon powder and carbon black is sintered together with a SiC powder raw material, and SiC raw material particles are bonded into a continuous porous ceramic support body by adopting the silicon-carbon reaction of a NaCl-KCl molten salt system. The surface of the silicon carbide ceramic membrane is provided with uniform pores formed by nanometer fibers interwoven by silicon carbide nanometer fibers. The process for preparing the silicon carbide ceramic membrane is simple and convenient, the sintering temperature is low, the content of oxides is low, and pores are uniform.
Aiming at the problems of high temperature, high equipment requirement, high energy consumption, large surface ceramic membrane pore size and the like in the prior art, the method highlights the sintering of the newly generated silicon carbide phase and the silicon carbide raw material, and the preparation of the silicon carbide ceramic support body is obtained.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention adopts silicon carbide powder, silicon powder, carbon black, naCl-KCl fused salt, kaolin, sodium carboxymethyl cellulose, PVP, glycerol, water and other raw materials to prepare the silicon carbide ceramic membrane through the processes of batching, mixing into mud, molding, drying, sintering, soaking in water to remove salt and the like.
The method bonds SiC raw material particles into a porous ceramic support body by means of a beta-SiC new phase generated by silicon and carbon solid phase reaction sintering and a molten salt liquid phase reaction, and prepares the silicon carbide ceramic membrane by coating and sintering silicon carbide nano-fiber slurry.
The method specifically comprises the following steps:
(1) Proportioning and kneading into mud, extruding and molding, and drying to prepare a dry biscuit: weighing silicon carbide powder, silicon powder, carbon powder, naCl-KCl fused salt, kaolin, carboxymethyl cellulose, glycerol and the like according to a formula, adding water, stirring and mixing the materials, kneading the materials into mud, extruding and molding the kneaded mud material, controlling the molding temperature to obtain a wet silicon carbide support body biscuit of a high-quality molded blank, and drying the wet silicon carbide support body biscuit in an oven to obtain a silicon carbide biscuit;
(2) Placing the dried silicon carbide biscuit in a high-temperature furnace, vacuumizing and heating to completely crack organic matters such as a bonding forming agent and the like in the silicon carbide biscuit and realize cracking and glue discharging;
(3) Sintering the silicon carbide support body: putting the silicon carbide biscuit into a sintering furnace, sintering at high temperature to obtain porous silicon carbide, soaking in water to remove salt, and obtaining a porous silicon carbide support;
(4) Mixing silicon carbide nanofibers and polyvinyl alcohol (PVA) according to a certain concentration to obtain a silicon carbide nanofiber aqueous slurry, coating the silicon carbide nanofiber aqueous slurry on a porous silicon carbide support, and drying the porous silicon carbide support coated with the slurry in an oven;
(5) And sintering the silicon carbide support body coated with the silicon carbide nano fibers in a high-temperature furnace to obtain the silicon carbide ceramic membrane.
In the step (1), the silicon powder and the carbon black are mixed in a ratio of 1: (1-3) mixing the raw materials in a molar ratio to obtain silicon-carbon composite powder, and uniformly mixing the raw materials by closed stirring, material mixing and other modes of a stirrer; then, mixing 70-80 parts by mass of silicon carbide powder, silicon-carbon composite powder, naCl-KCl fused salt, kaolin, carboxymethyl cellulose and glycerol: 6-15: 2 to 5:5 to 10:1 to 4:0.2 to 0.5.
Thus, the silicon carbide ceramic membrane is prepared by adding carbon black and silicon powder into the silicon carbide particles and sintering by utilizing low-temperature liquid phase reaction, so that the silicon carbide ceramic membrane has the characteristics of low sintering temperature, low oxide content, corrosion resistance, high strength and the like.
And the mixed raw material NaCl-KCl fused salt obtained in the step (1) has a refining effect on the raw powder, the ratio of the fused salt is 1.2, a fused salt method is adopted, naCl-KCl is used as a fused salt medium, and a Si powder and carbon react to generate a SiC new phase on the surface of the silicon carbide raw powder.
The grain diameter of the silicon carbide powder is 0.1-10 mu m, and the purity is more than 99%.
In the step (1), the concrete processes of adding water, stirring and mixing materials are as follows: the raw materials are dry-mixed for 10-30 min in a mixer, then water is added for wet mixing for 40-60 min, pugging is carried out, and the mixture is placed at normal temperature for aging for 24h.
In the step (1), drying is carried out in an oven according to the following specific step temperature control mode:
airing the mud blank at normal temperature for 12-24 h, transferring the mud blank into an oven, heating the mud blank to 50 ℃ from the normal temperature, wherein the heating rate is 1-5 ℃/min, and keeping the temperature for 3-5 h;
heating from 50 ℃ to 80 ℃, wherein the heating rate is 1-5 ℃/min, and keeping the temperature for 3-5 h;
heating from 80 ℃ to 120 ℃, wherein the heating rate is 1-5 ℃/min, and keeping the temperature for 5-10 h.
The step temperature control mode is adopted for drying treatment, cracks of the silicon carbide biscuit can be avoided, and the high-quality crack-free biscuit is prepared by gradually and slowly raising the temperature and volatilizing the moisture.
The step (2) is specifically as follows: and (3) placing the dried silicon carbide biscuit in a tube furnace, vacuumizing, and heating to 800 ℃ from the normal temperature at a heating rate of 3-5 ℃/min to completely crack organic matters such as a forming agent, a binder, a lubricant and the like in the silicon carbide biscuit.
Sintering aid is also added in the sintering in the step (3), and the sintering aid is kaolin or Al 2 O 3 With SiO 2 Composite powder.
In the step (3), the high-temperature sintering is specifically carried out according to the following specific step heating manner:
heating from normal temperature to 200 ℃, wherein the heating rate is 5-10 ℃/min, and keeping the temperature for 1-3 h;
heating from 200 ℃ to 900 ℃, wherein the heating rate is 5-10 ℃/min, and keeping the temperature for 1-3 h;
heating from 900 ℃ to 1350-1600 ℃, wherein the heating rate is 1-5 ℃/min;
preserving the heat for 1 to 5 hours at the temperature of 1350 to 1600 ℃;
and then cooling with the furnace.
The adoption of the stepped temperature control mode for high-temperature sintering treatment can control different temperatures to sequentially correspond to the formation of liquid phases in the high-temperature sintering process and the bonding among ceramic particles, thereby realizing the sintering of porous ceramics.
In the step (3), the step of soaking and desalting is to soak the porous silicon carbide in water for 30-60 min, then change the water, and repeat the process for 3-5 times.
And (4) preparing the silicon carbide nanofiber water slurry according to the concentration of 0.5-5 wt% of silicon carbide nanofiber and 0.2-0.5 wt% of polyvinyl alcohol in percentage by mass.
And (5) sintering the ceramic film in a high-temperature furnace at 900-1600 ℃ for 0.5-2 hours to obtain the silicon carbide ceramic film.
The sintering temperature of the support body is 1350-1600 ℃, because the raw materials contain silicon powder and carbon black, siC phase newly generated by the solid phase reaction of the silicon powder and the carbon black is co-sintered with SiC raw material powder to prepare the porous SiC ceramic, and meanwhile, the NaCl-KCl molten salt liquid phase is adopted to be beneficial to shaping, low-temperature sintering and pore forming of SiC raw material particles. The SiC raw material particles are adhered into a continuous porous ceramic support body through a beta-SiC new phase generated by the solid phase reaction and sintering of silicon and carbon and a molten salt liquid phase reaction, and nanopores constructed by interweaving SiC nanofibers are formed on the surface.
Aiming at the problems in the background technology, the invention adopts the raw materials containing silicon powder and carbon black, utilizes the SiC phase newly generated by the solid phase reaction of the silicon powder and the carbon black to be sintered together with the SiC powder raw material to prepare the porous SiC ceramic, and simultaneously adopts NaCl-KCl molten salt to be beneficial to the shaping, low-temperature sintering and pore forming of the SiC raw material. The SiC raw material particles are adhered into a continuous porous ceramic support body by a new beta-SiC phase generated by the solid phase reaction of silicon and carbon and a molten salt liquid phase reaction. The surface pores of the silicon carbide ceramic membrane coated with the silicon carbide nano fibers are constructed by the interwoven nano fibers, and the pores are small and uniform.
The invention has the beneficial effects that:
according to the invention, siC raw material particles are bonded into a continuous porous ceramic support body by adopting a silicon-carbon reaction of a NaCl-KCl molten salt system, and the silicon carbide nano-fiber is sintered at 900-1600 ℃, and the pores on the surface of the silicon carbide ceramic membrane coated with the silicon carbide nano-fiber are constructed by interweaved nano-fibers due to the bonding of PVA and the bonding of an oxide layer on the surface of the silicon carbide at high temperature, so that the pores are small and uniform. The sintering temperature is 1350-1600 ℃, the raw materials are easy to obtain, the preparation is simple, the molding is easy, the production cost is low, the requirement on a kiln is low, the energy consumption is low, and the method is suitable for preparing the porous silicon carbide ceramic material industrially customized.
The product of the invention has the characteristics of low oxide content, high purity, high porosity and acid and alkali resistance (the oxide content mainly depends on the addition amount of kaolin in the raw materials). The process has the advantages of low sintering temperature, simple forming process, low production cost, no need of ultrahigh temperature equipment and suitability for industrial large-scale production.
The porosity of the low-temperature reaction sintered silicon carbide ceramic film prepared by the invention is between 30 and 52 percent, and the volume density is between 1.0 and 1.5g/cm 3 The method has the characteristics of low sintering temperature, low oxide content, high internal porosity, nano-pores on the surface, acid and alkali resistance and the like.
Drawings
FIG. 1 is a flow chart of the preparation of the low-temperature reaction sintered silicon carbide ceramic film in example 1.
FIG. 2 is an SEM micrograph of a silicon carbide biscuit of example 1.
FIG. 3 is an SEM micrograph of a silicon carbide ceramic film of example 1.
Fig. 4 is an SEM micrograph of the silicon carbide nanowire ceramic film of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The examples of the invention are as follows:
example 1
(1) Proportioning and kneading into mud: silicon carbide powder, silicon-carbon composite powder, naCl-KCl fused salt, kaolin, carboxymethyl cellulose and glycerol are weighed according to a formula, and the mass ratio of the materials is 78:10:3:6:2.8:0.2. adding into a closed mixer, adding water, stirring, mixing, and kneading into mud.
Specifically, the raw materials are firstly dry-mixed in a mixer for 25min, then water is added for wet mixing for 50min, then pugging is carried out, and the mixture is placed at normal temperature for ageing for 24h.
(2) And (3) extrusion molding: extruding and molding the kneaded pug in an extrusion molding machine, controlling the molding temperature to be normal temperature, obtaining a wet silicon carbide support body biscuit, and cutting the biscuit into sheet pugs.
Then drying in a drying oven to obtain a silicon carbide biscuit;
(3) Drying and cracking the ceramic biscuit:
the wet silicon carbide support body mud blank is subjected to moisture removal and setting in an oven, and is specifically treated according to the following specific step temperature control mode:
airing the mud blank at normal temperature for 18h, then transferring the mud blank into an oven, heating the mud blank to 50 ℃ from the normal temperature, wherein the heating rate is 3 ℃/min, and keeping the temperature for 3h;
heating to 80 ℃ from 50 ℃, wherein the heating rate is 3 ℃/min, and keeping the temperature for 4h;
heating from 80 ℃ to 120 ℃, wherein the heating rate is 3 ℃/min, and keeping the temperature for 8h.
Drying to obtain a silicon carbide biscuit;
and (3) putting the dried silicon carbide biscuit into a tube furnace, vacuumizing, and raising the temperature to 800 ℃ from the normal temperature at the heating rate of 4 ℃/min to completely crack the forming agent and the lubricant in the silicon carbide biscuit.
(4) Sintering the silicon carbide support body: putting the biscuit after drying and cracking into a sintering furnace, wherein the sintering process comprises the following steps: heating from normal temperature to 600 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 600 ℃ to 900 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 900 deg.C to 1450 deg.C at a heating rate of 3 deg.C/min; keeping the temperature for 2 hours at 1450 ℃; then cooling along with the furnace;
and then placing the porous silicon carbide in water to soak for 40min, then changing the water, and repeating the above steps for 4 times to obtain the porous silicon carbide ceramic membrane.
(5) Preparing silicon carbide nanofiber slurry, laminating, drying and sintering: and (3) brushing silicon carbide nanofiber slurry prepared from silicon carbide nanofibers and polyvinyl alcohol PVA according to the mass percentages of 5wt% and 0.5wt% on the porous silicon carbide support, and drying the coated layer in an oven for 5 hours at 100 ℃.
(6) Sintering of the silicon carbide ceramic membrane: and sintering the silicon carbide support body coated with the silicon carbide nano fibers in a high-temperature furnace at 1200 ℃ for 2h to obtain the silicon carbide ceramic membrane.
The SEM microstructures of the silicon carbide ceramic membrane obtained in example 1 before and after sintering, and the silicon carbide nanofiber ceramic membrane are shown in fig. 2, 3 and 4, respectively. The porosity of the silicon carbide ceramic film obtained in example 2 was 40.5% and the bulk density was 1.25g/cm as calculated by the test 3 The oxide content is about 6%.
Example 2
(1) Proportioning and kneading into mud: weighing and mixing silicon carbide powder, silicon-carbon composite powder, naCl-KCl molten salt, kaolin, carboxymethyl cellulose and glycerol according to a formula, wherein the mass ratio of the materials is 70:14:2:10:3.5:0.5. adding into a closed mixer, adding water, stirring, mixing, and kneading into mud.
Specifically, the raw materials are firstly dry-mixed in a mixer for 30min, then are wet-mixed with water for 60min, and then are pugged and are placed at normal temperature for ageing for 24h.
(2) And (3) extrusion molding: extruding and molding the kneaded pug in a vacuum extrusion molding machine, controlling the molding temperature to obtain a wet silicon carbide support body biscuit, and cutting the biscuit into sheet pugs.
(3) Drying and cracking the ceramic biscuit:
the wet silicon carbide support body mud blank is subjected to moisture removal and setting in an oven, and is specifically treated according to the following specific step temperature control mode:
airing the mud blank at normal temperature for 24 hours, then transferring the mud blank into an oven, heating the mud blank to 50 ℃ from the normal temperature, wherein the heating rate is 5 ℃/min, and keeping the temperature for 3 hours;
heating from 50 ℃ to 80 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 5h;
heating from 80 ℃ to 120 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 10h.
Drying to obtain a silicon carbide biscuit;
and (3) putting the dried silicon carbide biscuit into a tube furnace, vacuumizing, and raising the temperature to 800 ℃ from the normal temperature at the heating rate of 4 ℃/min to completely crack the forming agent and the lubricant in the silicon carbide biscuit.
(4) Sintering the silicon carbide support body: putting the biscuit after drying and cracking into a sintering furnace, wherein the sintering process comprises the following steps: heating from normal temperature to 600 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 600 ℃ to 900 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 900 ℃ to 1450 ℃, wherein the heating rate is 3 ℃/min; keeping the temperature for 2 hours at 1450 ℃; then cooling along with the furnace;
and then placing the porous silicon carbide in water to soak for 60min, then changing the water, repeating the above steps for 5 times to obtain the porous silicon carbide ceramic membrane.
(5) Preparing silicon carbide nanofiber slurry, laminating, drying and sintering: and brushing silicon carbide nanofiber slurry prepared from 0.5wt% of silicon carbide nanofiber and 0.2wt% of polyvinyl alcohol PVA in percentage by mass on the porous silicon carbide support, and drying the coated layer in an oven at 100 ℃ for 5 hours.
(6) Sintering of the silicon carbide ceramic membrane: and sintering the silicon carbide support body coated with the silicon carbide nano fibers in a high-temperature furnace at 900 ℃ for 2 hours to obtain the silicon carbide ceramic membrane.
The silicon carbide ceramic film obtained in example 2 was found to have a porosity of 33.4% and a bulk density of 1.286g/cm 3 The oxide content is about 10%.
Example 3
(1) Proportioning and kneading into mud: weighing and mixing silicon carbide powder, silicon-carbon composite powder, naCl-KCl molten salt, kaolin, carboxymethyl cellulose and glycerol according to a formula, wherein the mass ratio of the materials is 75:12:2.5:6.5:3.7:0.3. adding into a closed mixer, adding water, stirring, mixing, and kneading into mud.
Specifically, the raw materials are firstly dry-mixed in a mixer for 10min, then water is added for wet mixing for 40min, then pugging is carried out, and the mixture is placed at normal temperature for ageing for 24h.
(2) And (3) extrusion molding: extruding and molding the kneaded pug in a vacuum extrusion molding machine, controlling the molding temperature to obtain a wet silicon carbide support body biscuit, and cutting the biscuit into sheet pugs.
(3) Drying and cracking the ceramic biscuit:
the wet silicon carbide support body mud blank is subjected to moisture removal and setting in an oven, and is specifically treated according to the following specific step temperature control mode:
airing the mud blank at normal temperature for 12h, then transferring the mud blank into an oven, heating the mud blank to 50 ℃ from the normal temperature, wherein the heating rate is 1 ℃/min, and keeping the temperature for 3h;
heating from 50 ℃ to 80 ℃, wherein the heating rate is 1 ℃/min, and keeping the temperature for 3h;
heating from 80 ℃ to 120 ℃, wherein the heating rate is 1 ℃/min, and keeping the temperature for 5h.
Drying to obtain a silicon carbide biscuit;
and (3) putting the dried silicon carbide biscuit into a tube furnace, vacuumizing, and raising the temperature to 800 ℃ from the normal temperature at the heating rate of 3 ℃/min to completely crack the forming agent and the lubricant in the silicon carbide biscuit.
(4) Sintering the silicon carbide support body: putting the biscuit after drying and cracking into a sintering furnace, wherein the sintering process comprises the following steps: heating from normal temperature to 600 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 600 ℃ to 900 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 900 ℃ to 1500 ℃, wherein the heating rate is 3 ℃/min; keeping the temperature for 2 hours at 1500 ℃; then cooling along with the furnace;
and then placing the porous silicon carbide in water for soaking for 30min, then changing the water, and repeating the steps for 5 times to obtain the porous silicon carbide ceramic membrane.
(5) Preparing silicon carbide nanofiber slurry, laminating, drying and sintering: and (2) brushing silicon carbide nanofiber aqueous slurry prepared from 2.5wt% of silicon carbide nanofiber and 0.3wt% of polyvinyl alcohol PVA on the porous silicon carbide support body, and drying the coated layer in an oven at 100 ℃ for 4 hours.
(6) Sintering the silicon carbide ceramic membrane: and sintering the silicon carbide support body coated with the silicon carbide nano fibers in a high-temperature furnace at 1000 ℃ for 2 hours to obtain the silicon carbide ceramic membrane.
The porosity of the silicon carbide ceramic film obtained in example 2 was 33.5% and the volume density was 1.29g/cm as calculated by the test 3 The oxide content is about 6.5%.
Example 4
(1) Proportioning and kneading into mud: silicon carbide powder, silicon-carbon composite powder, naCl-KCl fused salt, kaolin, carboxymethyl cellulose and glycerol are weighed according to a formula, and the mass ratio of the materials is 80:6:4:8:1.5:0.5. adding into a closed mixer, adding water, stirring, mixing, and kneading into mud.
Specifically, the raw materials are firstly dry-mixed for 20min in a mixer, then water is added for wet mixing for 45min, then pugging is carried out, and the mixture is placed at normal temperature for ageing for 24h.
(2) And (3) extrusion molding: extruding and molding the kneaded pug in a vacuum extrusion molding machine, controlling the molding temperature to obtain a wet silicon carbide support body biscuit, and cutting the biscuit into sheet pugs.
(3) Drying and cracking the ceramic biscuit: the wet silicon carbide support body mud blank is subjected to moisture removal and setting in an oven, and is specifically treated according to the following specific step temperature control mode:
airing the mud blank at normal temperature for 20 hours, then transferring the mud blank into an oven, heating to 50 ℃ from the normal temperature, keeping the temperature for 4 hours, wherein the heating rate is 4 ℃/min;
heating to 80 ℃ from 50 ℃, wherein the heating rate is 4 ℃/min, and keeping the temperature for 3h;
heating from 80 ℃ to 120 ℃, wherein the heating rate is 4 ℃/min, and keeping the temperature for 8h.
Drying to obtain a silicon carbide biscuit;
and (3) putting the dried silicon carbide biscuit into a tube furnace, vacuumizing, and raising the temperature to 800 ℃ from the normal temperature at the heating rate of 3 ℃/min to completely crack the forming agent and the lubricant in the silicon carbide biscuit.
(4) Sintering of the silicon carbide support body: putting the biscuit after drying and cracking into a sintering furnace, wherein the sintering process comprises the following steps: heating from normal temperature to 600 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 600 ℃ to 900 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 900 ℃ to 1500 ℃, wherein the heating rate is 3 ℃/min; keeping the temperature for 2 hours at 1500 ℃; then cooling along with the furnace;
and then placing the porous silicon carbide in water for soaking for 45min, then changing the water, and repeating the process for 4 times to obtain the porous silicon carbide ceramic membrane.
(5) Preparing silicon carbide nanofiber slurry, laminating, drying and sintering: and (3) brushing silicon carbide nanofiber and polyvinyl alcohol PVA (polyvinyl alcohol) on the porous silicon carbide support body according to the silicon carbide nanofiber aqueous slurry with the concentration of 0.4wt% in percentage by mass respectively, and then drying the coated layer in an oven for 5 hours at the temperature of 100 ℃.
(6) Sintering the silicon carbide ceramic membrane: and sintering the silicon carbide support body coated with the silicon carbide nano fibers in a high-temperature furnace at 1100 ℃ for 2 hours to obtain the silicon carbide ceramic membrane.
The silicon carbide ceramic film obtained in example 2 was found to have a porosity of 51.23% and a bulk density of 1.19g/cm 3 The oxide content is about 8%.
Example 5
(1) Proportioning and kneading into mud: silicon carbide powder, silicon-carbon composite powder, naCl-KCl fused salt, kaolin, carboxymethyl cellulose and glycerol are weighed according to a formula, and the mass ratio of the materials is 75:8:4:10:2.5:0.5. putting into a closed mixer, adding water, stirring and mixing, and kneading into mud.
Specifically, the raw materials are firstly dry-mixed in a mixer for 25min, then water is added for wet mixing for 40min, then pugging is carried out, and the mixture is placed at normal temperature for ageing for 24h.
(2) And (3) extrusion molding: extruding and molding the kneaded pug in a vacuum extrusion molding machine, controlling the molding temperature to obtain a wet silicon carbide support body biscuit, and cutting the biscuit into sheet pugs.
(3) Drying and cracking the ceramic biscuit: the wet silicon carbide support body mud blank is subjected to moisture removal and setting in an oven, and is specifically treated according to the following specific step temperature control mode:
airing the mud blank at normal temperature for 12h, then transferring the mud blank into an oven, heating the mud blank to 50 ℃ from the normal temperature, wherein the heating rate is 1 ℃/min, and keeping the temperature for 3h;
heating from 50 ℃ to 80 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 4h;
heating from 80 ℃ to 120 ℃, wherein the heating rate is 2 ℃/min, and keeping the temperature for 7h.
Drying to obtain a silicon carbide biscuit;
and (3) putting the dried silicon carbide biscuit into a tube furnace, vacuumizing, and raising the temperature to 800 ℃ from the normal temperature at the heating rate of 3 ℃/min to completely crack the forming agent and the lubricant in the silicon carbide biscuit.
(4) Sintering the silicon carbide support body: putting the biscuit after drying and cracking into a sintering furnace, wherein the sintering process comprises the following steps: heating from normal temperature to 600 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 600 ℃ to 900 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1h; heating from 900 ℃ to 1500 ℃, wherein the heating rate is 3 ℃/min; keeping the temperature for 2 hours at 1500 ℃; then cooling along with the furnace;
and then placing the porous silicon carbide in water to soak for 40min, then changing the water, and repeating the above steps for 4 times to obtain the porous silicon carbide ceramic membrane.
(5) Preparing silicon carbide nanofiber slurry, laminating, drying and sintering: and (3) brushing silicon carbide nanofiber and polyvinyl alcohol PVA (polyvinyl alcohol) on the porous silicon carbide support body according to the silicon carbide nanofiber aqueous slurry with the concentration of 0.4wt% in percentage by mass respectively, and then drying the coated layer in an oven for 5 hours at the temperature of 100 ℃.
(6) Sintering the silicon carbide ceramic membrane: and sintering the silicon carbide support body coated with the silicon carbide nano fibers in a high-temperature furnace at 1600 ℃ for 2 hours to obtain the silicon carbide ceramic membrane.
The porosity of the silicon carbide ceramic film obtained in example 2 was found to be 48.20% and the bulk density was found to be 1.20g/cm 3 The oxide content is about 10%.
Claims (7)
1. A preparation method of a low-temperature reaction sintered silicon carbide ceramic membrane is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) Proportioning and kneading into mud, extruding and molding, and drying to prepare a dry biscuit: weighing and mixing silicon carbide powder, silicon powder, carbon powder, naCl-KCl fused salt, kaolin, carboxymethyl cellulose and glycerol according to a formula, adding water, stirring and mixing the materials, kneading the materials into mud, extruding and molding the kneaded mud material, controlling the molding temperature to obtain a wet silicon carbide support body biscuit, and drying the wet silicon carbide support body biscuit in an oven to obtain a silicon carbide biscuit;
in the step (1), the silicon powder and the carbon black are mixed in a ratio of 1: (1 to 3) mixing the raw materials according to the molar ratio to obtain silicon-carbon composite powder; then, mixing 70-80 parts of silicon carbide powder, silicon-carbon composite powder, naCl-KCl fused salt, kaolin, carboxymethyl cellulose and glycerol in parts by weight: 6-15: 2 to 5:5 to 10:1 to 4:0.2 to 0.5;
(2) Placing the dried silicon carbide biscuit in a high-temperature furnace, and vacuumizing and heating;
(3) Putting the silicon carbide biscuit into a sintering furnace, sintering at high temperature to obtain porous silicon carbide, soaking in water to remove salt, and obtaining a porous silicon carbide support;
(4) Mixing silicon carbide nanofibers and polyvinyl alcohol (PVA) according to a certain concentration to obtain silicon carbide nanofiber water slurry, coating the silicon carbide nanofiber water slurry on a porous silicon carbide support, and drying the porous silicon carbide support coated with the slurry in an oven;
in the step (4), the silicon carbide nanofiber water slurry is prepared according to the concentration of 0.5wt% -5 wt% of silicon carbide nanofiber and 0.2wt% -0.5 wt% of polyvinyl alcohol in percentage by mass;
(5) And sintering the silicon carbide support body coated with the silicon carbide nano fibers in a high-temperature furnace to obtain the silicon carbide ceramic membrane.
2. The method for preparing a low-temperature reaction sintered silicon carbide ceramic film according to claim 1, wherein: in the step (1), the concrete processes of adding water, stirring and mixing materials are as follows: the raw materials are dry-mixed in a mixer for 10 to 30min, then water is added for wet mixing for 40 to 60min, pugging is carried out, and the mixture is placed at normal temperature for aging for 24 hours.
3. The method for preparing a low-temperature reaction sintered silicon carbide ceramic film according to claim 1, wherein: in the step (1), drying is carried out in an oven according to the following specific step temperature control mode:
airing the mud blank at normal temperature for 12 to 24h, then transferring the mud blank into an oven, heating the mud blank from the normal temperature to 50 ℃, wherein the heating rate is 1 to 5 ℃/min, and keeping the temperature for 3 to 5h;
heating from 50 ℃ to 80 ℃, wherein the heating rate is 1 to 5 ℃/min, and keeping the temperature for 3 to 5 hours;
heating from 80 ℃ to 120 ℃, wherein the heating rate is 1-5 ℃/min, and the heat preservation is 5-10 h.
4. The method for preparing a low-temperature reaction sintered silicon carbide ceramic film according to claim 1, wherein: the step (2) is specifically as follows: and (3) placing the dried silicon carbide biscuit in a tube furnace, vacuumizing, and heating to 800 ℃ from the normal temperature at a heating rate of 3-5 ℃/min for treatment.
5. The method for preparing a low-temperature reaction sintered silicon carbide ceramic film according to claim 1, wherein: in the step (3), the high-temperature sintering is specifically carried out according to the following specific step heating manner:
heating from normal temperature to 200 ℃, wherein the heating rate is 5 to 10 ℃/min, and the heat preservation is carried out for 1 to 3 hours;
heating from 200 ℃ to 900 ℃, wherein the heating rate is 5 to 10 ℃/min, and keeping the temperature for 1 to 3h;
heating from 900 ℃ to 1350-1600 ℃, wherein the heating rate is 1-5 ℃/min;
keeping the temperature at 1350 to 1600 ℃ for 1 to 5h;
and then cooling along with the furnace.
6. The method for preparing a low-temperature reaction sintered silicon carbide ceramic film according to claim 1, wherein: in the step (3), the step of soaking and desalting is to soak the porous silicon carbide in water for 30 to 60min, then change the water, and repeat the process for 3 to 5 times.
7. The method according to claim 1, wherein the method comprises the steps of: and (5) sintering the ceramic film in a high-temperature furnace at 900-1600 ℃ for 0.5-2 hours to obtain the silicon carbide ceramic film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111458282.6A CN113999046B (en) | 2021-12-02 | 2021-12-02 | Preparation method of low-temperature reaction sintered silicon carbide ceramic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111458282.6A CN113999046B (en) | 2021-12-02 | 2021-12-02 | Preparation method of low-temperature reaction sintered silicon carbide ceramic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113999046A CN113999046A (en) | 2022-02-01 |
| CN113999046B true CN113999046B (en) | 2023-03-10 |
Family
ID=79931086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111458282.6A Active CN113999046B (en) | 2021-12-02 | 2021-12-02 | Preparation method of low-temperature reaction sintered silicon carbide ceramic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113999046B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115093232A (en) * | 2022-07-08 | 2022-09-23 | 滁州学院 | Molecular sieve membrane support and preparation method thereof |
| CN115872761B (en) * | 2022-11-15 | 2023-08-29 | 湖南仁龙新材料有限公司 | Preparation method of silicon carbide smoke ceramic filter membrane |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130558A (en) * | 1997-10-29 | 1999-05-18 | Tokai Konetsu Kogyo Co Ltd | Porous silicon carbide sintered product and its production |
| CN101747078A (en) * | 2009-12-28 | 2010-06-23 | 黄黎敏 | Making method for sintering high-purity silicon carbide honeycomb ceramics by using nanometer silicon carbide as auxiliary |
| CN102295458A (en) * | 2011-06-10 | 2011-12-28 | 江苏大阳光辅股份有限公司 | Preparation method of reaction sinteredsilicon carbide ceramic |
| WO2012046897A1 (en) * | 2010-10-08 | 2012-04-12 | 성균관대학교 산학협력단 | Method for manufacturing porous silicon carbide ceramics |
| CN102503538A (en) * | 2011-11-02 | 2012-06-20 | 浙江大学 | Continuously pore-forming silicon carbide ceramic material and preparation method for same |
| CN104671788A (en) * | 2014-07-28 | 2015-06-03 | 上海柯瑞冶金炉料有限公司 | Method for sintering silicon carbide ceramic by in-situ synthetic nano SiC particle reinforcement reaction |
| CN105367058A (en) * | 2014-08-22 | 2016-03-02 | 上海柯瑞冶金炉料有限公司 | Method of sintering high-toughness silicon carbide ceramic by using vacuum reaction |
| CN105461306A (en) * | 2015-11-16 | 2016-04-06 | 石婷 | High-strength silicon carbide ceramic pipe and manufacturing method thereof |
| CN105541333A (en) * | 2015-12-10 | 2016-05-04 | 江西理工大学 | Preparation method for mullite in-situ reinforced silicon carbide porous ceramic sintered at low temperature |
| CN107663088A (en) * | 2017-08-03 | 2018-02-06 | 浙江理工大学 | A kind of preparation method of low-temperature sintering acid and alkali-resistance porous silicon carbide ceramic film |
| CN108329033A (en) * | 2018-01-26 | 2018-07-27 | 山东理工大学 | Liquid-phase sintering multichannel silicon carbide ceramics membrane component and preparation method thereof |
| 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 |
| CN109824381A (en) * | 2019-03-21 | 2019-05-31 | 武汉工程大学 | A kind of silicon carbide ceramic membrane and its preparation method and application |
| CN110698215A (en) * | 2019-10-29 | 2020-01-17 | 中国科学院上海硅酸盐研究所苏州研究院 | High-temperature-resistant corrosion-resistant reaction-sintered silicon carbide film support and preparation method thereof |
| CN111574226A (en) * | 2020-05-26 | 2020-08-25 | 潍坊盛润特种陶瓷有限公司 | Preparation method of high-density low-free silicon content reaction sintered silicon carbide ceramic material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007015550A1 (en) * | 2005-08-03 | 2007-02-08 | Ibiden Co., Ltd. | Jig for silicon carbide firing and method for producing porous silicon carbide body |
-
2021
- 2021-12-02 CN CN202111458282.6A patent/CN113999046B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130558A (en) * | 1997-10-29 | 1999-05-18 | Tokai Konetsu Kogyo Co Ltd | Porous silicon carbide sintered product and its production |
| CN101747078A (en) * | 2009-12-28 | 2010-06-23 | 黄黎敏 | Making method for sintering high-purity silicon carbide honeycomb ceramics by using nanometer silicon carbide as auxiliary |
| WO2012046897A1 (en) * | 2010-10-08 | 2012-04-12 | 성균관대학교 산학협력단 | Method for manufacturing porous silicon carbide ceramics |
| CN102295458A (en) * | 2011-06-10 | 2011-12-28 | 江苏大阳光辅股份有限公司 | Preparation method of reaction sinteredsilicon carbide ceramic |
| CN102503538A (en) * | 2011-11-02 | 2012-06-20 | 浙江大学 | Continuously pore-forming silicon carbide ceramic material and preparation method for same |
| CN104671788A (en) * | 2014-07-28 | 2015-06-03 | 上海柯瑞冶金炉料有限公司 | Method for sintering silicon carbide ceramic by in-situ synthetic nano SiC particle reinforcement reaction |
| CN105367058A (en) * | 2014-08-22 | 2016-03-02 | 上海柯瑞冶金炉料有限公司 | Method of sintering high-toughness silicon carbide ceramic by using vacuum reaction |
| CN105461306A (en) * | 2015-11-16 | 2016-04-06 | 石婷 | High-strength silicon carbide ceramic pipe and manufacturing method thereof |
| CN105541333A (en) * | 2015-12-10 | 2016-05-04 | 江西理工大学 | Preparation method for mullite in-situ reinforced silicon carbide porous ceramic sintered at low temperature |
| CN107663088A (en) * | 2017-08-03 | 2018-02-06 | 浙江理工大学 | A kind of preparation method of low-temperature sintering acid and alkali-resistance porous silicon carbide ceramic film |
| CN108329033A (en) * | 2018-01-26 | 2018-07-27 | 山东理工大学 | Liquid-phase sintering multichannel silicon carbide ceramics membrane component and preparation method thereof |
| 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 |
| CN109824381A (en) * | 2019-03-21 | 2019-05-31 | 武汉工程大学 | A kind of silicon carbide ceramic membrane and its preparation method and application |
| CN110698215A (en) * | 2019-10-29 | 2020-01-17 | 中国科学院上海硅酸盐研究所苏州研究院 | High-temperature-resistant corrosion-resistant reaction-sintered silicon carbide film support and preparation method thereof |
| CN111574226A (en) * | 2020-05-26 | 2020-08-25 | 潍坊盛润特种陶瓷有限公司 | Preparation method of high-density low-free silicon content reaction sintered silicon carbide ceramic material |
Non-Patent Citations (1)
| Title |
|---|
| SiC 纳米线增强反应烧结碳化硅陶瓷的性能研究;曾凡等;《硅酸盐通报》;20180228;第37卷(第2期);第586-590页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113999046A (en) | 2022-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113999046B (en) | Preparation method of low-temperature reaction sintered silicon carbide ceramic membrane | |
| CN107663088B (en) | Preparation method of low-temperature sintered acid-alkali-resistant porous silicon carbide ceramic membrane | |
| Liang et al. | Influencing factors on the performance of tubular ceramic membrane supports prepared by extrusion | |
| CN107619281B (en) | Preparation method of low-temperature sintered acid-alkali-resistant porous silicon carbide ceramic support | |
| WO2016037316A1 (en) | Preparation method of sic porous ceramic material and porous ceramic material manufactured by using same | |
| CN105254323B (en) | A kind of micropore corundum-mullite ceramics separation-membrane support and preparation method thereof | |
| CN107399989B (en) | Preparation method of reinforced silicon carbide-alumina composite foamed ceramic | |
| CN105884394B (en) | A kind of method of low-temperature preparation of porous carborundum supporter | |
| CN104072141B (en) | The preparation method of a kind of silicon carbide honeycomb ceramics | |
| CN108484149B (en) | Preparation method of NaA molecular sieve membrane support | |
| WO2017004776A1 (en) | Porous alumina ceramic ware and preparation method thereof | |
| CN113563103B (en) | Method for preparing gradient alumina porous ceramic by adopting tape casting forming method | |
| CN107082628B (en) | Preparation method of porous ceramic support based on molecular sieve membrane synthesis residual liquid | |
| CN108261928A (en) | Pure silicon carbide ceramics membrane component and preparation method thereof | |
| EP2105424B1 (en) | Method for manufacturing a honeycomb structured body | |
| CN110922204A (en) | Preparation method of low-temperature sintered alumina ceramic membrane | |
| Jiang et al. | Low-temperature sintering of a porous SiC ceramic filter using water glass and zirconia as sintering aids | |
| CN105272189A (en) | Microporous mullite ceramic separation membrane support and preparation method thereof | |
| CN113648848B (en) | Hollow flat ceramic membrane and preparation method thereof | |
| CN109020628A (en) | A kind of SiC nanowire enhancing porous ceramic composite and preparation method thereof | |
| CN1341578A (en) | Method for preparing silicon carbide porous ceramic pipe | |
| WO2024078182A1 (en) | Preparation method for ceramic fiber filter pipe with high air permeability | |
| CN109400203A (en) | A kind of preparation method of graphene inorganic porous ceramic film | |
| CN111804159B (en) | Silicon carbide whisker reinforced silicon carbide ceramic separation membrane based on tape casting and preparation method thereof | |
| CN105016773A (en) | Method for preparing porous silicon carbide ceramic through reactive sintering and micro-oxidation treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |