CN110922204B - Preparation method of low-temperature sintered alumina ceramic membrane - Google Patents
Preparation method of low-temperature sintered alumina ceramic membrane Download PDFInfo
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Abstract
The invention relates to the technical field of porous ceramic materials, in particular to a preparation method of a low-temperature sintered alumina ceramic membrane. The method is mainly characterized in that a sintering aid capable of sintering alumina ceramic within the temperature range of 1200-1300 ℃ is innovatively designed, the sintering temperature of the alumina porous ceramic material is obviously reduced due to the addition of the sintering aid, the sintering energy consumption and time are effectively saved, and a low-temperature sintered substrate and a low-temperature sintered film layer are provided for the production of the alumina ceramic film in the field of environmental protection. The preparation method has the characteristics of low sintering temperature, low production energy consumption, simple process method, low equipment requirement, low production cost and investment cost, flexible control, easy molding, suitability for industrial customization and capability of meeting large-scale production. The alumina ceramic membrane produced by the method has the characteristics of good hydrophilicity, super large permeation flux, high porosity, high yield, good acid and alkali resistance and long service life.
Description
Technical Field
The invention relates to the technical field of inorganic ceramic porous materials, in particular to the technical field of inorganic ceramic separation membrane materials, and specifically relates to a preparation method of a low-temperature sintered alumina ceramic membrane.
Background
The separation membrane material is the core of the membrane separation technology, the existing separation membrane material is mainly divided into an organic polymer membrane and an inorganic ceramic membrane, and compared with the organic polymer membrane material, the inorganic ceramic membrane material has the advantages of high mechanical strength, acid and alkali resistance, high temperature resistance, organic solvent resistance, biological corrosion resistance, oxidant oxidation resistance, narrow pore size distribution, high porosity, good pore concentration, good hydrophilicity, strong pollution resistance, long service life, wide application range and the like. Is particularly suitable for the fields of seawater desalination, wastewater treatment and reclamation, reclaimed water reuse, drinking water purification and the like, and is the separation material with the greatest development prospect at present.
However, in addition to the above advantages, the ceramic membrane has a significant disadvantage that the preparation process of the ceramic membrane is complicated and the manufacturing cost is high. The main reasons for the high cost of the ceramic membrane are long process flow, secondary sintering or multiple sintering, high sintering temperature, long heating and heat preservation time, longer cooling time and the like, so that the production period of the ceramic membrane is long and the yield of the membrane product is low. Patent application No. 201610329412.9 discloses a sintering method of alumina ceramics, wherein the sintering temperature is up to 1700 ℃; patent No. 201710280509.X discloses a method for preparing alumina ceramic membrane for sewage treatment, which has sintering temperature up to 1400 ℃ and needs protection environment in oxygen-free and inert atmosphere; patent application No. 201711351472.1 also reports that the sintering temperature of an alumina ceramic membrane needs to reach 1400 ℃. According to the reports of the preparation methods of various alumina ceramic membranes, the temperature required for sintering the alumina ceramic membranes is as high as 1400 ℃, fuel or electric energy required at high temperature is large, the time required for heating is long, and the energy consumption is large, so that the manufacturing cost of the ceramic membranes is greatly increased, and the high cost-performance ratio of the ceramic membranes is lost due to the excellent separation performance of the ceramic membranes. Therefore, lowering the sintering temperature of alumina ceramic membranes is a concern and must be addressed by the alumina ceramic industry.
Disclosure of Invention
The invention aims to solve the problems of high sintering temperature, high manufacturing cost, high investment cost and the like of the conventional alumina ceramic membrane. The preparation method of the low-temperature sintered alumina ceramic membrane has the technical advantages that the alumina porous ceramic membrane material with high porosity and high mechanical strength can be fired in a low-temperature environment (1200-1250 ℃) and an air atmosphere; the technical core is the sintering aid suitable for combining the alumina powder together in a low-temperature environment and an air atmosphere. The formula of the sintering bonding agent has low thermal expansion coefficient, the thermal expansion coefficient is matched with that of alumina powder, a liquid-phase melting agent is formed at low temperature, so that contact points of the alumina particles are bonded together, and pores are formed at non-contact positions, so that the porous alumina ceramic membrane is prepared. The method has the advantages of simple manufacturing process, low manufacturing cost and investment cost, low sintering temperature, high yield and large permeation flux, is suitable for industrial customization and meets the requirement of large-scale production.
In order to solve the problem of high-temperature sintering of the alumina ceramic support body in the preparation process, the technical scheme of the invention is as follows:
a process for preparing low-temp sintered ceramic alumina membrane from alpha-Al as raw material2O3Powder, sintering aid, plasticizer, pore-forming agent, plasticizer and lubricantA lubricant and a solvent, wherein: alpha-Al used as base material2O3The particle diameter range is 0.5-50 μm, and the film layer adopts alpha-Al2O3The particle size range is 0.1-0.5 μm; the sintering aid is composed of kaolin, magnesium oxide, calcium carbonate, silicon micropowder, high borosilicate glass powder and water glass, and the sintering aid is composed of the following components in percentage by mass (30-40 wt%): (15 wt% -25 wt%): (5 wt% -15 wt%): (15 wt% -25 wt%): (5 wt% -15 wt%): (1 wt% -10 wt%) and the sum of the mass percentages of all the components is 100%, and the sintering aid is the technical core of low-temperature sintering of the alumina ceramic support body and has the functions of forming a molten liquid phase at 1200-1250 ℃, bonding mutually contacted parts among alumina powder particles and forming a continuous solid solution with the alumina powder. The plasticizer is composed of one or more of water-soluble high molecular polymers such as methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose and polyvinyl alcohol, the aqueous solution of the plasticizer has certain viscosity, mainly has the function of sticking particles of alumina powder, sintering aid and other barren materials together, and can form a mud blank with a certain shape through the interaction of extrusion force of an extruder and a mould at normal temperature; the pore-forming agent is composed of one or more of starch, graphite, bamboo powder and cellulose, and has the function of being oxidized at high temperature to generate carbon dioxide gas, so that certain pores are formed among alumina powder particles, and the porosity of the alumina support body is improved; the plasticizer is composed of one or more of glycerol, polyethylene glycol, polyvinyl alcohol and polyacrylic acid, and has the functions of preventing the extruded mud blank from losing water in the aging process, and continuously keeping a plastic shape without cracking or warping; the lubricant is composed of one or more of oleic acid, tung oil, aluminum stearate and graphite, and has the functions of enhancing the fluidity among particles and reducing the abrasion between the particles and a die in the extrusion process; the dispersing agent is composed of one or more of polyacrylic acid, polyacrylamide, sodium polyacrylate, polyphosphoric acid, potassium stearate and ammonium citrate, and has the function of uniformly dispersing alumina powder in the film layer slurry in a solvent to prevent rapid sedimentation; the solvent is water or ethanolOr mixture of water and ethanol, and extruding the raw material and sintering aid in an extruder;
through the combination of the raw materials and the cooperation of a reasonable drying and sintering system, the alumina ceramic substrate and the film layer with simple forming process, low sintering temperature, high mechanical strength and large porosity can be obtained, and the preparation method comprises the following steps:
(1) substrate preparation
Alumina powder with the particle size range of 1-50 mu m, a sintering aid, a plasticizer, a pore-forming agent, a plasticizer, a lubricant and a solvent are mixed according to the mass percentage (95-75 wt%): (25 wt% to 5 wt%): (1 wt% -10 wt%): (1 wt% -10 wt%): (0.5 wt% to 5 wt%): (1 wt% -10 wt%): (10 wt% -30 wt%) and mixing, wherein the sum of the mass percentages of all the components except the solvent is 100%; adding various raw materials in the following sequence and operation in the operation process of the powerful mixer: alumina powder, plasticizer, sintering aid, pore-forming agent, solvent with plasticizer dissolved and lubricant which are mixed in proportion; each raw material is added, the raw materials are required to be mixed for 1-10 min, the temperature is not more than 34 ℃ in the material mixing process, otherwise, the plasticizing agent loses viscosity and cannot play a plasticizing role; kneading the mixture in a kneader for 10-60 min, wherein the temperature is not more than 34 ℃ in the kneading process; pugging for 1-3 times on a coarse pugging machine with cooling water, and then pugging for one time under the vacuum degree of not less than-0.095 MPa; ageing for 12-72 hours at the temperature of 20-25 ℃ and the humidity of 50-80%; extruding and molding according to design requirements, and processing single-channel tubular, multi-channel flat plate and multi-channel tubular alumina support bodies; the vacuum degree of the extruder is more than-0.095 MPa, the extrusion speed is 0.1-5 m/min, and the extrusion pressure is 1-10 MPa for extrusion molding; cutting into required length, transferring to continuous microwave for rapid shaping, adjusting the power of each box body within the range of 300-850W, and controlling the speed of a conveyor belt to be 0.5-5 m/min; then transferring the mixture into a blast drying oven, and drying the mixture for 1 to 24 hours at the temperature of between 50 and 120 ℃; transferring the dried biscuit to one of a high-temperature resistance furnace, a gas shuttle or drawer type kiln and a gas tunnel kiln, degumming and firing in an air atmosphere; the firing system is controlled as follows: removing the adsorption water from the room temperature to 200 ℃ at the heating rate of 20-50 ℃/h; keeping the temperature for 1-5 h at the temperature rising rate of 10-30 ℃/h from 200-550 ℃, and carrying out a degumming procedure; the temperature rise rate is 5-10 ℃/h from 550-600 ℃, and phase change cracking is avoided; heating to form a molten mass from 600 ℃ to a sintering temperature at a heating rate of 10-30 ℃/h; the firing temperature range is 1100-1300 ℃, the heat preservation is carried out for 3-5 h, the molten liquid phase is completely generated, and the heat balance of the whole kiln is achieved; then naturally cooling to room temperature to obtain a base material of the low-temperature sintered alumina ceramic;
(2) film preparation
alpha-Al having a particle diameter of 0.1 to 0.5 μm2O3The powder, the sintering aid, the binder, the dispersant and the solvent are prepared according to the following mass percentage (50-10 wt%): (0.1 wt% to 5 wt%): (0.1 wt% to 5 wt%): (0.1 wt% to 2 wt%): (50 wt% -90 wt%) and mixing, wherein the sum of the mass percentages of the components is 100%; the sintering aid is the same as the sintering aid in the step (1); the adhesive is composed of one or more of methylcellulose, sodium carboxymethylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose and polyvinyl alcohol; the dispersant is composed of one or more of polyacrylic acid, polyacrylamide, sodium polyacrylate, polyphosphoric acid, potassium stearate and ammonium citrate; the solvent is one or more of water, ethanol or a mixture of water and ethanol; uniformly mixing the raw materials in proportion, and performing ball milling for 1-12 hours to obtain slurry with uniform dispersion and good ductility; uniformly coating the prepared slurry on the base material prepared in the step (1) by adopting a spraying or dip-coating process, transferring the base material to a box-type microwave dryer, wherein the microwave power is 300-850W, and the microwave time is 0.2-1 h, or transferring the base material to a blast drying oven, and drying the base material for 1-4 h at the temperature of 80-120 ℃; and finally transferring the powder to one of a high-temperature resistance furnace, a gas shuttle or drawer type kiln and a gas tunnel kiln, sintering the powder in an air atmosphere, and controlling the sintering system as follows: the temperature is raised from room temperature to 150 ℃ at a rate of 10-30 ℃/min; the temperature rise rate is 20-50 ℃/min from 150-550 ℃; the temperature is increased at the rate of 5-10 ℃/min at the temperature of 550-600 ℃, the temperature is kept for 1-3 h, and cracking caused by phase change is avoided; 400-film layer firingThe temperature is increased at a rate of 20-50 ℃/min; firing temperature ranges from 1000 ℃ to 1200 ℃, and heat preservation is carried out for 1-3 h; and then naturally cooling to room temperature to obtain the ceramic membrane of the low-temperature sintered alumina.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the raw material name and the mass percentage are that the raw material comprises 1-50 mu m of alumina powder, sintering aid, plasticizer, pore-forming agent, plasticizer, lubricant and solvent according to the mass percentage (95-75 wt%): (25 wt% to 5 wt%): (1 wt% -10 wt%): (1 wt% -10 wt%): (0.5 wt% to 5 wt%): (1 wt% -10 wt%): (10 wt% -30 wt%) and the sum of the mass percentages of all the components except the solvent is 100%.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the sintering aid comprises the following raw materials in percentage by mass, wherein the raw materials comprise kaolin, magnesium oxide, calcium carbonate, silica powder, high borosilicate glass powder and water glass, and the raw materials comprise, by mass, (30-40%): (15 wt% -25 wt%): (5 wt% -15 wt%): (15 wt% -25 wt%): (5 wt% -15 wt%): (1 wt% -10 wt%) and the sum of the mass percentages of all the components is 100%.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the shape of the multi-channel flat plate type and the multi-channel tube type channels is one or the combination of more than one of square, rectangle, circle, ellipse and rhombus.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the extrusion parameters are that the vacuum degree of the extruder is more than-0.095 MPa, the extrusion speed is 0.1-5 m/min, and the extrusion pressure is 1-10 MPa.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the rapid shaping and drying parameters are that the power of each box body of continuous microwaves is adjusted within the range of 300-850W, and the speed of a conveyor belt is 0.5-5 m/min; and drying the mixture for 1-24 hours in a blast drying oven at 50-120 ℃.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the firing system is controlled as follows: the temperature is raised from room temperature to 200 ℃ at a rate of 20-50 ℃/h; keeping the temperature for 1-5 h from 200-550 ℃ at the heating rate of 10-30 ℃/h; the temperature rise rate is 5-10 ℃/h from 550-600 ℃; the temperature rise rate is 10-30 ℃/h from 600-1250 ℃; preserving heat for 3-5 h at 1100-1300 ℃; then naturally cooling to room temperature.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the raw material name and the mass percentage of the film layer slurry are alpha-Al with the particle size range of 0.1-0.5 mu m2O3The powder, the sintering aid, the adhesive, the dispersant and the solvent are mixed according to the mass percentage (50-10 percent): (0.1 wt% to 5 wt%): (0.1 wt% to 5 wt%): (0.1 wt% to 2 wt%): (50 wt% -90 wt%) and mixing, wherein the sum of the mass percentages of all the components is 100%.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the dispersant is one or more of polyacrylic acid, polyacrylamide, sodium polyacrylate, polyphosphoric acid, potassium stearate and ammonium citrate.
Preferably, the preparation method of the low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the control program of the film sintering is as follows: the temperature is raised from room temperature to 150 ℃ at a rate of 10-30 ℃/min; the temperature rise rate is 20-50 ℃/min from 150-550 ℃; the temperature is increased at the rate of 5-10 ℃/min at the temperature of 550-600 ℃, the temperature is kept for 1-3 h, and cracking caused by phase change is avoided; 400-film layer firing temperature, wherein the heating rate is 20-50 ℃/min; firing temperature ranges from 1000 ℃ to 1200 ℃, and heat preservation is carried out for 1-3 h; then naturally cooling to room temperature.
The technical scheme of the preparation method of the low-temperature sintered alumina ceramic membrane has the following beneficial effects:
1. the low-temperature sintered alumina ceramic membrane is sintered by oxidizing flame at a lower temperature of 1250 ℃ and a lower temperature of 1150 ℃ and an oxidizing flame sintering membrane layer in an air atmosphere, so that the method has the advantages of low sintering temperature, low production energy consumption, simple process method, low equipment requirement, low production cost and low investment cost.
2. The low-temperature sintered alumina ceramic membrane adopts a high-temperature melting liquid-phase sintering method, the technical core is the formula of a sintering aid, the results of the raw material screening and proportion optimization of the formula are matched with the thermal expansion coefficient of alumina, and the problems of cracking, warping and surface defects in the firing process can be avoided.
3. The invention has reasonable selection of the base material and the film layer particles, a transition layer is not needed between the pore diameter of the base material sintered and the film layer powder, and the powder of the film layer can not permeate into the base material to block the pore diameter of the base material, thereby simplifying the sintering process, saving the preparation time and the preparation energy consumption.
4. According to the method for sintering the alumina ceramic membrane at the low temperature, the sintered product has the properties of high mechanical strength, large porosity, acid and alkali resistance, high temperature resistance, oxidant resistance, thermal shock resistance and the like.
Drawings
FIG. 1 is a schematic cross-sectional view of a square-channel flat alumina ceramic membrane.
FIG. 2 is a schematic cross-sectional view of a single-channel tubular alumina ceramic membrane.
FIG. 3 is a schematic cross-sectional view of a multi-channel tubular alumina ceramic membrane.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, which are not intended to limit the scope of the present disclosure in any way.
Example 1
85% alpha-Al with a medium particle size of 5 mu m2O3Mixing powder, 15% of sintering aid (35% of kaolin, 20% of magnesium oxide, 10% of calcium carbonate, 20% of silicon micropowder, 10% of borosilicate glass powder and 5% of water glass), 5.5% of hydroxypropyl methyl cellulose (viscosity is 10 ten thousand), 6% of graphite powder (5000 meshes), 6% of oleic acid and 22% of water (containing 2 per thousand of polyacrylic acid dissolved in water) in a powerful mixer for 40 min; kneading in a kneader for 30 min; pugging for 1-3 times on a rough pugging machine, and then pugging for one time under the vacuum degree of not less than-0.095 MPa; ageing for 24 hours at the temperature of 20-25 ℃ and the humidity of 50-80%; then pugging once again under the vacuum degree of not less than-0.095 MPa;extruding a multi-pore channel tubular alumina support body on an extruder with the vacuum degree of not less than-0.095 MPa, wherein the outer diameter of the support body is 30mm, the pore channel is 19, and the diameter of the pore channel is 4 mm; continuous microwave rapid shaping is carried out, wherein the microwave power is 600w, the speed of a conveyor belt is 1.5m/min, and the microwave is carried out for two times; drying for 12h in a resistance hot air drying box at 110 ℃; sintering at high temperature in a natural gas drawer type kiln, wherein the high-temperature kiln is controlled by the program of controlling the temperature to be between room temperature and 200 ℃ and the heating rate to be 30 ℃/h; keeping the temperature for 3 hours from 200-550 ℃ with the heating rate of 20 ℃/h; the temperature rise rate is 8 ℃/h from 550-600 ℃; the temperature rise rate is 20 ℃/h from 600 ℃ to 1250 ℃; preserving the heat for 3 hours at 1250 ℃; naturally cooling to room temperature to obtain the multi-channel tubular alumina substrate.
40% of alpha-Al with the grain diameter range of 0.3 mu m2O3Uniformly mixing powder, 5% of sintering aid, 1% of adhesive, 2% of dispersant and 50% of solvent, ball-milling for 1-12 h to obtain slurry with uniform dispersion and good ductility, uniformly coating the prepared slurry on the substrate prepared in the step (1) by adopting a spraying or dip-coating process, transferring to a box-type microwave dryer, performing microwave power of 600W and microwave time of 0.5h, or transferring to a resistance hot air dryer, and performing heat preservation for 2h at 110 ℃; and finally, transferring the powder to a high-temperature resistance kiln, a gas shuttle kiln, a drawer type kiln or a tunnel kiln, and sintering in an air atmosphere, wherein the sintering control procedure is as follows: the temperature is raised from room temperature to 150 ℃ at the rate of 20 ℃/min; the temperature rise rate is 30 ℃/min from 150-550 ℃; the temperature is increased at the rate of 8 ℃/min at the temperature of 550-600 ℃, the temperature is kept for 1.5h, and cracking caused by phase change is avoided; 400-film layer sintering temperature, and the heating rate is 40 ℃/min; the sintering temperature is 1150 ℃, and the temperature is kept for 1.5 h; then naturally cooling to room temperature to obtain the alumina ceramic membrane.
Example 2
Except that the firing temperature of the film layer was changed to 1100 deg.C, the other operation steps, the amounts of addition, and the control parameters were the same as those in example 1.
Example 3
Except that the firing temperature of the film layer was changed to 1120 ℃, the other operation steps, the amount of addition, and the control parameters were the same as those of example 1.
Example 4
Except that the firing temperature of the film layer was changed to 1180 ℃, the other operation steps, the amount of addition, and the control parameters were the same as those in example 1.
Example 5
Except that the firing temperature of the film layer was changed to 1200 ℃, the other operation steps, the amount of addition, and the control parameters were the same as those in example 1.
The method for evaluating the performance of the ceramic support prepared by the invention is shown in the table 1:
table 2 ceramic support performance testing in the above examples:
the above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (3)
1. A preparation method of a low-temperature sintered alumina ceramic membrane is characterized by comprising the following steps: the raw material comprises alpha-Al2O3The preparation method comprises the following steps of (1) preparing powder, a sintering aid, a plasticizer, a pore-forming agent, a plasticizer, a lubricant, a binder, a dispersant and a solvent;
the sintering aid is composed of kaolin, magnesium oxide, calcium carbonate, silicon micropowder, high borosilicate glass powder and water glass, and is composed of the following components in percentage by mass (30-40 wt%): (15 wt% -25 wt%): (5 wt% -15 wt%): (15 wt% -25 wt%): (5 wt% -15 wt%): (1 wt% -10 wt%) and the sum of the mass percentages of the components is 100%;
the plasticizer is one or more of methyl cellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, or polyvinyl alcohol which are easily soluble in water;
the pore-forming agent is composed of one or more of starch, graphite, bamboo powder and cellulose;
the plasticizer is composed of one or more of glycerol, polyethylene glycol, polyvinyl alcohol, or polyacrylic acid;
the lubricant is composed of one or more of oleic acid, tung oil, aluminum stearate or graphite;
the adhesive is composed of one or more of methylcellulose, sodium carboxymethylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, or polyvinyl alcohol;
the dispersant is composed of one or more of polyacrylic acid, polyacrylamide, sodium polyacrylate, polyphosphoric acid, potassium stearate or ammonium citrate;
the solvent is one or more of water, ethanol or a mixture of water and ethanol;
the preparation method comprises the following specific steps:
(1) substrate preparation
alpha-Al having a particle diameter of 1 to 50 μm2O3The sintering aid comprises powder, a sintering aid, a plasticizer, a pore-forming agent, a plasticizer, a lubricant and a solvent, wherein the mass percentage of the powder is (95-75 wt%): (25 wt% -5 wt%): (1 wt% -10 wt%): (1 wt% -10 wt%): (0.5 wt% to 5 wt%): (1 wt% -10 wt%): (10 wt% -30 wt%) mixing; the sum of the mass percentages of all the components except the solvent is 100 percent; then mixing, kneading, pugging, extruding, drying and sintering to obtain a low-temperature sintered alumina ceramic substrate;
mixing, kneading, pugging, extruding, drying and sintering in the preparation process of the base material, and adding various raw materials in the following sequence and operation in the operation process of a powerful mixer: alumina powder, plasticizer, sintering aid, pore-forming agent, plasticizer-dissolving solvent and lubricant which are mixed in proportion;
each raw material is added, the raw materials are required to be mixed for 1-10 min, and the temperature is not more than 34 ℃ in the mixing process;
kneading in a kneader for 10-60 min, wherein the temperature in the kneading process does not exceed 34 ℃;
pugging for 1-3 times on a coarse pugging machine with cooling water, and then pugging for one time under the vacuum degree of not less than-0.095 MPa;
ageing for 12-72 hours at the temperature of 20-25 ℃ and the humidity of 50-80%; extruding and molding according to design requirements, and processing single-channel tubular, multi-channel flat plate and multi-channel tubular alumina substrates; the vacuum degree of the extruder is more than-0.095 MPa, the extrusion speed is 0.1-5 m/min, and the extrusion pressure is 1-10 MPa for extrusion molding;
then transferring the mixture into a blast drying oven, and drying the mixture for 1 to 24 hours at the temperature of between 50 and 120 ℃; transferring the dried biscuit to one of a high-temperature resistance furnace, a gas shuttle or drawer type kiln and a gas tunnel kiln, degumming and firing in an air atmosphere;
(2) film preparation
alpha-Al having a particle diameter of 0.1 to 0.5 μm2O3The powder, the sintering aid, the adhesive, the dispersant and the solvent are mixed according to the mass percentage (50-10 percent): (0.1 wt% to 5 wt%): (0.1 wt% to 5 wt%): (0.1 wt% to 2 wt%): (50 wt% -90 wt%) and mixing, wherein the sum of the mass percentages of the components is 100%; the sintering aid is the same as the sintering aid in the step (1); uniformly mixing the raw materials in proportion, and performing ball milling for 1-12 hours to obtain slurry with uniform dispersion and good ductility; then coating, drying and sintering treatment are carried out, and the low-temperature sintered alumina ceramic membrane can be obtained;
coating, drying and sintering in the preparation process of the film layer, uniformly coating the prepared slurry on the base material prepared in the step (1) by adopting a spraying or dip-coating process, and transferring the base material into a box-type microwave dryer, wherein the microwave power is 300-850W, the microwave time is 0.2-1 h,
or transferring the mixture into a blast drying oven, and drying the mixture for 1 to 4 hours at the temperature of between 80 and 120 ℃; then transferring the powder to one of a high-temperature resistance furnace, a gas shuttle or drawer type kiln and a gas tunnel kiln for sintering in air atmosphere;
the sintering system is controlled as follows: the temperature is raised from room temperature to 150 ℃ at a rate of 10-30 ℃/min; the temperature rise rate is 20-50 ℃/min from 150-550 ℃; the temperature is 550-600 ℃, the heating rate is 5-10 ℃/min, and the temperature is kept for 1-3 h; 400-film layer firing temperature, wherein the heating rate is 20-50 ℃/min; firing temperature ranges from 1000 ℃ to 1200 ℃, and heat preservation is carried out for 1-3 h; then naturally cooling to room temperature.
2. The method for preparing a low-temperature sintered alumina ceramic membrane according to claim 1, wherein: after extrusion molding, cutting the materials into required lengths, transferring the materials into continuous microwaves for rapid shaping, adjusting the power of each box body within the range of 300-850W, and controlling the speed of a conveyor belt to be 0.5-5 m/min.
3. The method for preparing a low-temperature sintered alumina ceramic membrane according to claim 1, wherein: the extrusion molding die is one of a single-channel tube type, a multi-channel flat plate type and a multi-channel tube type.
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| CN111704439A (en) * | 2020-06-05 | 2020-09-25 | 江苏埃梯恩膜过滤技术有限公司 | Ceramic pug of flat ceramic membrane for tap water treatment and preparation method |
| CN111662073A (en) * | 2020-06-05 | 2020-09-15 | 江苏埃梯恩膜过滤技术有限公司 | Ceramic pug of large-flow tubular ceramic membrane and preparation method |
| CN114249582B (en) * | 2020-09-25 | 2023-01-10 | 三达膜科技（厦门）有限公司 | Internal multi-runner disc type alumina ceramic membrane and preparation method thereof |
| CN113149679A (en) * | 2021-03-16 | 2021-07-23 | 南京航空航天大学 | Alumina porous ceramic for air bearing and preparation method thereof |
| CN115364677B (en) * | 2021-05-21 | 2024-03-19 | 三达膜科技（厦门）有限公司 | Preparation method of thermal stability modified spherical alumina ceramic microfiltration membrane |
| CN113336529B (en) * | 2021-07-12 | 2023-01-31 | 南京九思高科技有限公司 | Multi-channel water-in-oil type emulsion membrane and preparation method thereof |
| CN115321959A (en) * | 2022-08-22 | 2022-11-11 | 广东环波新材料有限责任公司 | Environment-friendly LTCC ceramic slurry and substrate preparation method |
| CN116023120A (en) * | 2023-02-28 | 2023-04-28 | 西安工程大学 | Coal gasification fine slag-based inorganic ceramic membrane and preparation method thereof |
| CN116835996B (en) * | 2023-07-03 | 2024-03-26 | 威海智洁环保技术有限公司 | Preparation method of low-temperature sintered anti-pollution ceramic membrane |
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