CN111233507A - Porous yttria-stabilized zirconia water-based rolled film and preparation method thereof - Google Patents
Porous yttria-stabilized zirconia water-based rolled film and preparation method thereof Download PDFInfo
- Publication number
- CN111233507A CN111233507A CN202010202023.6A CN202010202023A CN111233507A CN 111233507 A CN111233507 A CN 111233507A CN 202010202023 A CN202010202023 A CN 202010202023A CN 111233507 A CN111233507 A CN 111233507A
- Authority
- CN
- China
- Prior art keywords
- stabilized zirconia
- yttria
- water
- rolling
- blank
- 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.)
- Pending
Links
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
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- 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
-
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
- C04B35/6365—Cellulose or derivatives thereof
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a porous yttria-stabilized zirconia water-based rolled film and a preparation method thereof, wherein the preparation method comprises the following steps: and (3) refining mud: adding a binder aqueous solution accounting for 40-100% of the weight of the yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring, and then extruding and pugging the mixture to obtain pug blocks; rolling: continuously rolling the mud block to obtain blank sheets with smooth and flat surfaces, and then gradually rolling the blank sheets to 0.5-1 mm; and (3) drying: drying the blank sheet at room temperature to constant weight; punching: stamping the dried blank sheet to obtain a green blank sheet; rubber discharging and sintering: heating the green sheet to 800-. The method can effectively solve the problems of complex preparation process, single product shape, uneven product internal pores and low yield existing in the conventional method.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a porous yttria-stabilized zirconia water-based rolled film and a preparation method thereof.
Background
The Solid Oxide Fuel Cell (SOFC) belongs to the third-generation Cell, has lower manufacturing cost, can achieve higher catalytic efficiency by only adopting a nickel (Ni) catalyst without using a noble metal catalyst, has strong Fuel adaptability, and can adopt hydrogen as Fuel, liquid ethanol, hydrocarbon and even Solid carbon as Fuel. The SOFC mainly has two structure types of a flat plate and a tubular, and different structure types need to adopt a preparation process matched with the structure types. In comparison, the flat SOFC has the advantages of low cost, simple forming process and the like.
8% (mole fraction) Y2O3Stabilized ZrO2(YSZ) is widely used as an electrolyte of SOFC due to its unique properties such as high chemical stability, thermal stability and pure ionic conductivity under various conditions, and porous YSZ is generally used for an anode or cathode frame, and is generally formed by dry pressing, tape casting, extrusion, electrochemical vapor deposition, chemical vapor deposition, physical vapor deposition, sputtering, sol-gel, screen printing, and the like.
The YSZ ceramic material prepared by the above-mentioned forming method is limited in the difficulty of the forming process, the manufacturing cost, the shape of the sample, the size of the product, and the like, for example: the microstructure of a sample prepared by dry pressing is not uniform, and the size and shape of the prepared sample are single, so that a large-size sample cannot be prepared; the tape casting mostly adopts binary organic solution as solvent, which not only has high cost and can cause serious pollution to the environment, but also has complex process formula, thus leading to large molding difficulty and low yield of the product; the extrusion molding is mainly used for preparing tubular ceramic products, the molding process is complex, the molding method is easy to have the problems of nonuniform microstructure caused by insufficient water retention, deformation, cracking and the like of the products; electrochemical vapor deposition, chemical vapor deposition, physical vapor deposition can be used to obtain thin films, but they have disadvantages of relatively low deposition rate, expensive equipment, and generation of corrosive gases; the sputtering method can prepare a film, but the growth speed is slow (<1 μm/h); the film obtained by the sol-gel coating technology has to be repeatedly operated in the drying and heating processes to obtain the pinhole-free film for the SOFC, and the repeated operation causes the production period to be prolonged; the screen printing method has high requirements on parameters such as the particle size, the grain shape, the surface property, the filling density and the like of the powder.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a porous yttria-stabilized zirconia water-based rolled film, which can effectively solve the problems of complex preparation process, single product shape, uneven product internal pores and low yield existing in the conventional method.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a porous yttria-stabilized zirconia water-based rolled film comprises the following steps:
(1) and (3) refining mud: adding a binder aqueous solution accounting for 40-100% of the weight of the yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring, and then extruding and pugging the mixture to obtain pug blocks;
(2) rolling: continuously rolling the mud blocks in the step (1) to obtain blank sheets with smooth and flat surfaces, and then gradually rolling the blank sheets to 0.5-1 mm;
(3) and (3) drying: drying the blank sheet obtained in the step (2) at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: heating the green sheet obtained in the step (4) to 800-.
The beneficial effects produced by adopting the scheme are as follows: the yttria-stabilized zirconia powder is uniformly mixed by the water-based binder, so that the pollution of an organic solvent to the environment can be reduced, the environment friendliness is improved, and the water-based binder is lower in price, so that the cost is controlled. The yttria-stabilized zirconia is sequentially subjected to pugging, sheet rolling, drying and sheet punching to form a green sheet with uniform internal materials, the discharge of a binder and a plasticizer in the green sheet can be promoted in the process of slowly raising the temperature of the green sheet at a proper speed, the deformation of the green sheet can be prevented, the forming rate of the green sheet is improved, the decomposition and discharge of the binder and the plasticizer in the green sheet can be further promoted in the process of heat preservation at the temperature of 800-1000 ℃, and a porous structure is initially formed in the green sheet in the process of gradually decomposing and discharging the binder and the plasticizer, so that the foundation is laid for the subsequent formation of a porous structure; in the process of continuously cooling at a proper speed, the discharge of residual binder and plasticizer can be further promoted, and meanwhile, a porous structure can be formed in the process of cooling, so that the problem of cracking of the blank sheets can be avoided at the proper cooling speed, and the quality of the blank sheets is improved; finally, in the process of heat preservation of the blank sheet at 1300-1400 ℃, the particles with smaller pores formed in the blank sheet are sintered into a whole, the small pores are sintered, and the larger pores are reserved, so that the formed porosity and the uniformity of the pores are improved.
Further, the weight of the binder solution in step (1) was 74% of the weight of the yttria-stabilized zirconia powder.
The beneficial effects produced by adopting the scheme are as follows: the yttria-stabilized zirconia and the binder aqueous solution are mixed according to a proper proportion, so that the mixing uniformity can be ensured, the time for subsequent mud refining can be reduced, and the preparation time can be shortened.
Further, the preparation method of the aqueous binder solution in the step (1) is as follows: dissolving methyl cellulose in hot water of 60-90 ℃, adding cold water of 1/3 times of the volume of the hot water, stirring uniformly, cooling to room temperature, adding a plasticizer, and stirring uniformly to obtain the product.
The beneficial effects produced by adopting the scheme are as follows: the hot water can promote the methyl cellulose to be melted into gel, the melting time is accelerated, the cooling of the gel can be accelerated in the process of adding cold water into the gel, the gel is dissolved in a water body after being cooled to form a solution, and then the dissolving speed of the plasticizer can be accelerated when the plasticizer is added into the gel.
Further, the weight ratio of the water, the methyl cellulose and the plasticizer in the aqueous binder solution in the step (1) is 100:1-36: 15-65.
Further, the weight ratio of the water, the methylcellulose and the plasticizer in the aqueous binder solution in the step (1) is 100:27: 40.
The beneficial effects produced by adopting the scheme are as follows: the proper proportion of the binder and the plasticizer can improve the powder mixing effect and the strength and plasticity of the prepared mud block. Because the average molecular weight of the methyl cellulose is larger, after a proper amount of methyl cellulose is added, the space occupied by the methyl cellulose among yttria-stabilized zirconia powder is increased, after high-temperature sintering, a binding agent is decomposed, a large amount of pores can be generated, a porous structure is formed, and then a structure with higher porosity can be prepared under the condition of not adding a pore-forming agent.
Further, the methylcellulose type number is 400 or 1500.
Further, the methylcellulose type number is 1500.
Further, the plasticizer is one or more of polyvinyl alcohol, glycerol, polyethylene glycol and dibutyl phthalate.
The beneficial effects produced by adopting the scheme are as follows: suitable plasticizers can improve plasticity and shorten flaking time.
Further, the solid content of the clod obtained in step (1) was 57%.
The beneficial effects produced by adopting the scheme are as follows: when the content of the solid content is low, the plasticity of the mud block is too strong, the blank is easy to deform after the sheet rolling, the content of the solid content is too high, and the plasticity of the mud block is too low, so that the sheet rolling forming is not facilitated.
Further, the heat preservation time in the step (5) is 1-3h under the conditions of 800-.
Further, in the step (5), the temperature of the green sheet is increased to 900 ℃ at the speed of 1 ℃/min, the temperature is maintained for 1h, then the temperature is decreased to 25 ℃ at the speed of 5 ℃/min, and then the green sheet is placed at 1300 ℃ for the temperature to be maintained for 5h, so that the ceramic material is prepared.
The beneficial effects produced by adopting the scheme are as follows: heating to 800-1000 ℃ and preserving heat for 1-3h, which can promote the discharge of the binder and the plasticizer and promote the formation of pores in the blank; the heat preservation is carried out for 3-5h under the conditions of 1300 ℃ and 1400 ℃, so that the excessive deformation of the particles can be avoided, and the excessive porosity can be avoided.
The beneficial effects produced by the invention are as follows:
1. the preparation method has the advantages of simple and convenient operation, short production period, low production cost, high yield and high porosity, and is suitable for large-scale production.
2. According to the invention, methyl cellulose with a large molecular weight is used as a binder, a proper amount of methyl cellulose solution is added to uniformly mix powder, the methyl cellulose is uniformly distributed in the blank, the methyl cellulose is decomposed and discharged in the process of gradually increasing the temperature at a certain speed, pores with a certain size are formed in the blank, the purpose of pore-forming is realized on the premise of not adding a pore-forming agent, the discharge can be promoted in the process of increasing the temperature and reducing the temperature at a certain speed, meanwhile, the problems of deformation and cracking of the blank can be avoided, the pores in the blank can be integrated in the process of sintering at a high temperature to form porcelain, so that the smaller pores disappear, and the uniformity of the pores is improved.
Detailed Description
Example 1
A porous yttria-stabilized zirconia water-based rolled film is prepared by the following steps:
(1) and (3) refining mud: dissolving methylcellulose in hot water at 60 ℃, adding cold water with the volume being 1/3 times that of the hot water, uniformly stirring, cooling to room temperature, adding glycerol, and uniformly stirring to obtain an adhesive aqueous solution, wherein the weight ratio of water to methylcellulose to glycerol is 100:36:43, and the viscosity of the methylcellulose is 400; adding a binder aqueous solution accounting for 60% of the weight of yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring to obtain a premix, putting the premix between two press rollers of a film rolling machine, extruding and mixing the premix through the rolling rotation of the press rollers, blowing air onto the premix during the rolling to accelerate the volatilization of water, so that a mud block can be rapidly formed into a film preliminarily, and a mud block with a solid content of 62.5% is obtained;
(2) rolling: continuously rolling the mud blocks in the step (1) on a press roll of a film rolling machine to obtain blank sheets with smooth and flat surfaces and no air bubbles inside, then cutting the edges of the blank sheets orderly, gradually reducing the distance between the two press rolls, and gradually rolling the blank sheets to 1mm from thick to thin;
(3) and (3) drying: cutting the edges of the blank sheet obtained in the step (2) again to be tidy, and then drying at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: and (4) heating the green sheet obtained in the step (4) to 900 ℃ at the speed of 1.5 ℃/min, preserving heat for 1h, then cooling to 20 ℃ at the speed of 5 ℃/min, and then preserving heat for 3h at the temperature of 1300 ℃ to obtain the product.
Example 2
A porous yttria-stabilized zirconia water-based rolled film is prepared by the following steps:
(1) and (3) refining mud: dissolving methyl cellulose in hot water of 90 ℃, adding cold water with the volume being 1/3 times that of the hot water, uniformly stirring and cooling to room temperature, adding glycerol and polyethylene glycol, and uniformly stirring to prepare a binder aqueous solution, wherein the weight ratio of the water to the methyl cellulose to the glycerol to the polyethylene glycol is 100:36:28:15, and the viscosity of the methyl cellulose is 400; adding a binder aqueous solution accounting for 50% of the weight of yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring to obtain a premix, putting the premix between two press rollers of a film rolling machine, extruding and mixing the premix through the rolling rotation of the press rollers, blowing air onto the premix during the rolling to accelerate the volatilization of water, so that the pug can be rapidly formed into a film preliminarily, and a pug block with the solid content of 66.7% is obtained;
(2) rolling: continuously rolling the mud blocks in the step (1) on a press roll of a film rolling machine to obtain blank sheets with smooth and flat surfaces and no air bubbles inside, then cutting the edges of the blank sheets orderly, gradually reducing the distance between the two press rolls, and gradually rolling the blank sheets to 1mm from thick to thin;
(3) and (3) drying: cutting the edges of the blank sheet obtained in the step (2) again to be tidy, and then drying at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: and (3) heating the green sheet obtained in the step (4) to 800 ℃ at the speed of 1 ℃/min, preserving heat for 2h, then cooling to 30 ℃ at the speed of 5 ℃/min, and then preserving heat for 4h at 1350 ℃ to obtain the ceramic material.
Example 3
A porous yttria-stabilized zirconia water-based rolled film is prepared by the following steps:
(1) and (3) refining mud: dissolving methyl cellulose by using hot water with the temperature of 80 ℃, then adding cold water with the volume being 1/3 times of that of the hot water, uniformly stirring and cooling to room temperature, adding glycerol, and uniformly stirring to prepare an adhesive aqueous solution, wherein the weight ratio of water to the methyl cellulose to a plasticizer is 100:29:52, and the viscosity of the methyl cellulose is 1500; adding a binder aqueous solution accounting for 68.7 percent of the weight of yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring to obtain a premix, putting the premix between two press rollers of a film rolling machine, extruding and mixing the premix through the rolling rotation of the press rollers, blowing air onto the premix during the rolling to accelerate the volatilization of water, so that the mud can be rapidly formed into a film preliminarily, and obtaining a mud block with the solid content of 59 percent;
(2) rolling: continuously rolling the mud blocks in the step (1) on a press roll of a film rolling machine to obtain blank sheets with smooth and flat surfaces and no air bubbles inside, then cutting the edges of the blank sheets orderly, gradually reducing the distance between the two press rolls, and gradually rolling the blank sheets to 1mm from thick to thin;
(3) and (3) drying: cutting the edges of the blank sheet obtained in the step (2) again to be tidy, and then drying at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: and (4) heating the green sheet obtained in the step (4) to 1000 ℃ at the speed of 1.5 ℃/min, preserving heat for 1h, then cooling to 25 ℃ at the speed of 3 ℃/min, and then preserving heat for 5h at the temperature of 1400 ℃ to obtain the product.
Example 4
A porous yttria-stabilized zirconia water-based rolled film is prepared by the following steps:
(1) and (3) refining mud: dissolving methyl cellulose by using hot water at 70 ℃, adding cold water with the volume being 1/3 times that of the hot water, uniformly stirring and cooling to room temperature, adding glycerol and polyvinyl alcohol, and uniformly stirring to obtain a binder aqueous solution, wherein the weight ratio of the water to the polyvinyl alcohol to the methyl cellulose to the glycerol is 100:3:27:36, and the viscosity of the methyl cellulose is 1500; adding a binder aqueous solution accounting for 74% of the weight of yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring to obtain a premix, putting the premix between two press rollers of a film rolling machine, extruding and mixing the premix through the rolling rotation of the press rollers, blowing air onto the premix during the rolling to accelerate the volatilization of water, so that the pug can be rapidly formed into a film preliminarily, and a mud block with the solid content of 57% is obtained;
(2) rolling: continuously rolling the mud blocks in the step (1) on a press roll of a film rolling machine to obtain blank sheets with smooth and flat surfaces and no air bubbles inside, then cutting the edges of the blank sheets orderly, gradually reducing the distance between the two press rolls, and gradually rolling the blank sheets to 1mm from thick to thin;
(3) and (3) drying: cutting the edges of the blank sheet obtained in the step (2) again to be tidy, and then drying at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: and (4) heating the green sheet obtained in the step (4) to 900 ℃ at the speed of 1 ℃/min, preserving heat for 1h, then cooling to 25 ℃ at the speed of 5 ℃/min, and then preserving heat for 5h under the condition of 1300 ℃ to obtain the product.
Comparative example 1
A porous yttria-stabilized zirconia water-based rolled film is prepared by the following steps:
(1) and (3) refining mud: mixing yttria-stabilized zirconia powder and a pore-forming agent, carrying out ball milling to obtain slurry, and baking the slurry to obtain porous yttria-stabilized zirconia powder, wherein the weight ratio of yttria-stabilized zirconia to the pore-forming agent is as follows: mixing polyvinyl alcohol, a plasticizer and deionized water, heating and stirring until the polyvinyl alcohol, the plasticizer and the deionized water are completely dissolved, and then naturally cooling to room temperature to prepare a binder aqueous solution, wherein the weight ratio of water to polyvinyl alcohol to glycerol is 100:33: 40; adding a binder aqueous solution accounting for 57% of the weight of yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring to obtain a premix, putting the premix between two press rollers of a film rolling machine, extruding and mixing the premix through the rolling rotation of the press rollers, blowing air onto the premix during the rolling to accelerate the volatilization of water, so that the pug can be rapidly formed into a film preliminarily, and a mud block with the solid content of 64% is obtained;
(2) rolling: continuously rolling the mud blocks in the step (1) on a press roll of a film rolling machine to obtain blank sheets with smooth and flat surfaces and no air bubbles inside, then cutting the edges of the blank sheets orderly, gradually reducing the distance between the two press rolls, and gradually rolling the blank sheets to 1mm from thick to thin;
(3) and (3) drying: cutting the edges of the blank sheet obtained in the step (2) again to be tidy, and then drying at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: and (4) heating the green sheet obtained in the step (4) to 900 ℃ at the speed of 3 ℃/min, preserving heat for 2h, then cooling to 20 ℃ at the speed of 4 ℃/min, and then preserving heat for 5h under the condition of 1300 ℃ to obtain the product.
Comparative example 2
A porous yttria-stabilized zirconia water-based rolled film is prepared by the following steps:
(1) and (3) refining mud: and (3) refining mud: mixing polyvinyl alcohol, a plasticizer and deionized water, heating and stirring until the polyvinyl alcohol, the plasticizer and the deionized water are completely dissolved, and then naturally cooling to room temperature to prepare a binder aqueous solution, wherein the weight ratio of water to polyvinyl alcohol to glycerol is 100:33: 40; adding a binder aqueous solution accounting for 57% of the weight of yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring to obtain a premix, putting the premix between two press rollers of a film rolling machine, extruding and mixing the premix through the rolling rotation of the press rollers, blowing air onto the premix during the rolling to accelerate the volatilization of water, so that the pug can be rapidly formed into a film preliminarily, and a mud block with the solid content of 64% is obtained;
(2) rolling: continuously rolling the mud blocks in the step (1) on a press roll of a film rolling machine to obtain blank sheets with smooth and flat surfaces and no air bubbles inside, then cutting the edges of the blank sheets orderly, gradually reducing the distance between the two press rolls, and gradually rolling the blank sheets to 1mm from thick to thin;
(3) and (3) drying: cutting the edges of the blank sheet obtained in the step (2) again to be tidy, and then drying at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: and (4) heating the green sheet obtained in the step (4) to 900 ℃ at the speed of 6 ℃/min, preserving heat for 4h, then cooling to 20 ℃ at the speed of 8 ℃/min, and then preserving heat for 3h at the temperature of 1400 ℃ to obtain the product.
Comparative example 3
A porous yttria-stabilized zirconia water-based rolled film is prepared by the following steps:
(1) and (3) refining mud: dissolving methyl cellulose in hot water of 70 ℃, adding cold water with the volume being 1/3 times that of the hot water, uniformly stirring, cooling to room temperature, adding glycerol, and uniformly stirring to obtain a binder aqueous solution, wherein the weight ratio of water to methyl cellulose to glycerol is 100:40:60, and the viscosity of the methyl cellulose is 400; adding a binder aqueous solution accounting for 100% of the weight of yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring to obtain a premix, putting the premix between two press rollers of a film rolling machine, extruding and mixing the premix through the rolling rotation of the press rollers, blowing air onto the premix during the rolling to accelerate the volatilization of water, so that the pug can be rapidly formed into a film preliminarily, and obtaining a pug block with the solid content of 50%;
(2) rolling: continuously rolling the mud blocks in the step (1) on a press roll of a film rolling machine to obtain blank sheets with smooth and flat surfaces and no air bubbles inside, then cutting the edges of the blank sheets orderly, gradually reducing the distance between the two press rolls, and gradually rolling the blank sheets to 1mm from thick to thin;
(3) and (3) drying: cutting the edges of the blank sheet obtained in the step (2) again to be tidy, and then drying at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: and (4) heating the green sheet obtained in the step (4) to 1100 ℃ at the speed of 8 ℃/min, preserving heat for 1h, then cooling to 20 ℃ at the speed of 4 ℃/min, and then preserving heat for 2h at the temperature of 1550 ℃ to obtain the ceramic.
Examples of the experiments
The sizes of the pores, the porosities and the yields of the rolled films prepared in examples 1 to 5 and comparative examples 1 to 3 were respectively detected and calculated, and the specific detection method of the pores was: the Archimedes drainage method comprises the following steps of: ρ ═ m1/(m3-m2)，ρr＝ρ/ρthX 100%, the specific test results are shown in Table 1.
Table 1: porosity and yield statistical table
From the above table, it can be seen that the rolled films prepared according to the method of the present invention (examples 1 to 4) have uniform and well-distributed internal pore sizes and high porosity and yield, and especially the rolled film prepared according to the method of example 4 has the best quality. The rolled film prepared according to the method in comparative example 1 can obtain a blank sheet with high porosity on the premise of using a pore-forming agent, but the uniformity degree of pores is not good; in the common comparison of comparative examples 1 and 2, the rolled film obtained by the method of comparative example 2 had low porosity, varied pore size and non-uniform distribution, indicating that the green sheet could not be made porous without the use of the polyvinyl alcohol binder as the pore former. The rolled film prepared by the method in the comparative example 3 has large pores, and the fact that the added methylcellulose has too large amount, large pores are formed in the subsequent heating discharge process, the pores are too large, the solid content is reduced, and the rolled film quality cannot meet the requirements is proved.
Claims (10)
1. A preparation method of a porous yttria-stabilized zirconia water-based rolled film is characterized by comprising the following steps:
(1) and (3) refining mud: adding a binder aqueous solution accounting for 40-100% of the weight of the yttria-stabilized zirconia powder into the yttria-stabilized zirconia powder, uniformly stirring, and then extruding and pugging the mixture to obtain pug blocks;
(2) rolling: continuously rolling the mud blocks in the step (1) to obtain blank sheets with smooth and flat surfaces, and then gradually rolling the blank sheets to 0.5-1 mm;
(3) and (3) drying: drying the blank sheet obtained in the step (2) at room temperature to constant weight;
(4) punching: stamping the blank sheet dried in the step (3) to obtain a blank sheet;
(5) rubber discharging and sintering: heating the green sheet obtained in the step (4) to 800-.
2. The method of claim 1, wherein the binder solution in step (1) is present in an amount of about 74% by weight of the yttria-stabilized zirconia powder.
3. The method of preparing a porous yttria-stabilized zirconia water-based rolled film according to claim 1, wherein the aqueous binder solution in step (1) is prepared by: dissolving methyl cellulose in hot water of 60-90 ℃, adding cold water of 1/3 times of the volume of the hot water, stirring uniformly, cooling to room temperature, adding a plasticizer, and stirring uniformly to obtain the product.
4. The method of claim 3, wherein the aqueous binder solution of step (1) comprises water, methylcellulose, and plasticizer in a weight ratio of 100:15 to 36:15 to 65.
5. The method for producing a porous yttria-stabilized zirconia water-based rolled film according to claim 3 or 4, wherein the weight ratio of the water, the methylcellulose and the plasticizer in the aqueous binder solution in the step (1) is 100:27: 40.
6. The method of preparing a porous yttria-stabilized zirconia water-based rolled film according to claim 3 or 4, wherein the methylcellulose type number is 400 or 1500.
7. The method of claim 3, wherein the plasticizer is one or more of polyvinyl alcohol, glycerol, polyethylene glycol, and dibutyl phthalate.
8. The method for preparing a porous yttria-stabilized zirconia water-based rolled film according to claim 3, wherein the solid content of the cake obtained in the step (1) is 57%.
9. The method for preparing a porous yttria-stabilized zirconia water-based rolled film according to claim 6, wherein the green sheet in the step (5) is prepared by raising the temperature to 900 ℃ at a speed of 1 ℃/min, preserving the temperature for 1h, then lowering the temperature to 25 ℃ at a speed of 5 ℃/min, and preserving the temperature for 5h at 1300 ℃.
10. A porous yttria stabilised zirconia water based rolled film produced by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010202023.6A CN111233507A (en) | 2020-03-20 | 2020-03-20 | Porous yttria-stabilized zirconia water-based rolled film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010202023.6A CN111233507A (en) | 2020-03-20 | 2020-03-20 | Porous yttria-stabilized zirconia water-based rolled film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111233507A true CN111233507A (en) | 2020-06-05 |
Family
ID=70869412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010202023.6A Pending CN111233507A (en) | 2020-03-20 | 2020-03-20 | Porous yttria-stabilized zirconia water-based rolled film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111233507A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343175A (en) * | 2008-08-20 | 2009-01-14 | 哈尔滨工业大学 | Aluminum oxide/aluminium titanate porous ceramic and preparation thereof |
| US20150132549A1 (en) * | 2012-05-11 | 2015-05-14 | Keranor As | Green Ceramic Tapes and Method for Their Fabrication |
| CN104987107A (en) * | 2015-07-16 | 2015-10-21 | 神华集团有限责任公司 | Composition for filtering ceramic production, filtering ceramic, and preparation method and application of filtering ceramic |
| CN106891420A (en) * | 2017-02-20 | 2017-06-27 | 广东东方锆业科技股份有限公司 | A kind of method that rolling formation makes zirconia ceramic product |
| CN107686379A (en) * | 2017-07-25 | 2018-02-13 | 歌尔股份有限公司 | The preparation method of zirconia ceramics with porous layer |
| CN110240492A (en) * | 2018-03-07 | 2019-09-17 | 海加尔(厦门)科技有限公司 | A kind of preparation method of the ceramic separation film supporter of acid and alkali-resistance |
-
2020
- 2020-03-20 CN CN202010202023.6A patent/CN111233507A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343175A (en) * | 2008-08-20 | 2009-01-14 | 哈尔滨工业大学 | Aluminum oxide/aluminium titanate porous ceramic and preparation thereof |
| US20150132549A1 (en) * | 2012-05-11 | 2015-05-14 | Keranor As | Green Ceramic Tapes and Method for Their Fabrication |
| CN104987107A (en) * | 2015-07-16 | 2015-10-21 | 神华集团有限责任公司 | Composition for filtering ceramic production, filtering ceramic, and preparation method and application of filtering ceramic |
| CN106891420A (en) * | 2017-02-20 | 2017-06-27 | 广东东方锆业科技股份有限公司 | A kind of method that rolling formation makes zirconia ceramic product |
| CN107686379A (en) * | 2017-07-25 | 2018-02-13 | 歌尔股份有限公司 | The preparation method of zirconia ceramics with porous layer |
| CN110240492A (en) * | 2018-03-07 | 2019-09-17 | 海加尔(厦门)科技有限公司 | A kind of preparation method of the ceramic separation film supporter of acid and alkali-resistance |
Non-Patent Citations (1)
| Title |
|---|
| 吴其胜: "《材料物理性能》", 31 December 2018, 华东理工大学 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hedayat et al. | Review on fabrication techniques for porous electrodes of solid oxide fuel cells by sacrificial template methods | |
| CN103875109B (en) | The preparation method of the tubular type ceramic structure of non-circular cross sections | |
| KR101553627B1 (en) | Process for producing tubular ceramic structures | |
| CN100466355C (en) | Electrolyte sheet with protruding features having undercut angles and method of separating such sheet from its carrier | |
| CN104258737A (en) | Preparation method of large-size thin-wall hollow flat-plate ceramic film | |
| Morales et al. | Processing of graded anode-supported micro-tubular SOFCs based on samaria-doped ceria via gel-casting and spray-coating | |
| CN111509251B (en) | Bipolar plate for hydrogen fuel cell and preparation method thereof | |
| CN100433438C (en) | Method for producing anode-supporting solid oxide fuel cell | |
| Navarro et al. | Manufacturing of anode-supported tubular solid oxide fuel cells by a new shaping technique using aqueous gel-casting | |
| Durango-Petro et al. | Ascendable method for the fabrication of micro-tubular solid oxide fuel cells by ram-extrusion technique | |
| KR101222867B1 (en) | Anode support using spherical pore former and solid oxide fuel cell and the fabrication method therefor | |
| CN111384408B (en) | Porous anode support body of solid oxide fuel cell and preparation method thereof | |
| CN111233507A (en) | Porous yttria-stabilized zirconia water-based rolled film and preparation method thereof | |
| JP2014516461A (en) | Method for preparing electrochemical half-cell | |
| Seo et al. | Study of Microextrusion Printing for Enlarging Electrode–Electrolyte Interfacial Area in Anode-Supported SOFCs | |
| CN102244274A (en) | Process method for preparing electrodes of molten carbonate fuel cell by use of wet method | |
| CN107845822B (en) | Fuel cell anode support extrusion pug and preparation method thereof | |
| CN115947614B (en) | Titanium dioxide ceramic electrode, preparation method and application thereof, and electric equipment | |
| CN111348912A (en) | Solid oxide fuel cell dense electrolyte and preparation method thereof | |
| CN1233057C (en) | Method for preparing strontium lanthanum manganate self-supporting tube of solid oxide fuel cell by utiling slip-casting process | |
| CN107658486B (en) | Preparation method of solid oxide fuel cell electrolyte membrane | |
| CN115417660B (en) | Eu (Eu) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof | |
| JPH06290799A (en) | Manufacture of electrolytic sheet for fused carbonate type fuel cell | |
| CN113381047A (en) | High-temperature oxide ion conductor battery and preparation method thereof | |
| CN114204044A (en) | Preparation method of supported anode in anode-supported solid oxide fuel cell with symmetrical structure |
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 |