JPH0192397A - Production of membranous ceramic - Google Patents

Abstract

PURPOSE:To produce the title membranous ceramic of intricate shape and an extremely thin membranous ceramic by forming an electrodeposition coating film contg. the raw ceramic material on an electrically conductive material, curing the film, then releasing the film from the material, and calcining the material. CONSTITUTION:The electrically conductive material of Al, etc., with one side masked is electrodeposition-coated in a suspension contg. the electrodeposition paint contg. the raw ceramic material consisting of an oxide such as zirconia, a carbide such as silicon carbide, a nitride such as silicon nitride, etc. The coated material is washed with water, and then dried to cure the coating film. The masking tape is then released from the material, and the Al material is completely dissolved by an aq. NaOH soln. to release the coating film. The obtained material is washed with water and then dried, the binder is removed in a calcining furnace, and the material is sintered. By this method, a green compact contg. a large amt. of resinous components, highly flexible, and easy to handle can be obtained. Consequently, an extremely thin membranous ceramic having the intricate shape corresponding to the shape of the material can be easily obtained.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a method for manufacturing membrane ceramics.

Conventional technology and its problems Conventionally, as a raw material composition for producing a film-like ceramic molded body, a mixture of a ceramic raw material and a polymer compound as a binder mixed with an organic solvent or water has been used. There is. Generally, as a method for producing a film-like ceramic molded body using such a composition, the raw material composition is formed into a film by a doctor blade method, an extrusion method, a roll method, etc., and then a solvent or A method is adopted in which water is evaporated to produce a molded body with appropriate shape retention (hereinafter referred to as a green molded body), and then this green molded body is fired to obtain the desired ceramic molded body. .

However, such a manufacturing method has the following problems.

■ The ceramic molded bodies produced are limited to sheet-like ones, and complicated shapes such as pipe-like shapes cannot be obtained.

■ When the amount of binder is increased, the viscosity of the kneaded product becomes high. For this reason, there is a limit to the amount of binder added;
It is difficult to obtain a green molded body with a film thickness of microns or less.

Means for Solving the Problems In view of the above-mentioned current situation, the present inventors have proposed a method for easily producing membrane-like ceramics having various shapes such as pipe shapes, and which has a very thick film. We have been conducting intensive research to find a method that can produce thin film ceramics. As a result, a conductive material is immersed in an electrodeposition paint containing ceramic raw materials for electrodeposition coating, and the resulting electrodeposition coating is then cured and peeled off from the conductive material, followed by firing. Alternatively, the electrodeposited coating film is cured and then fired to form a ceramic layer on the conductive material, and then this ceramic layer is peeled off from the conductive material to form the ceramic film. Depending on the method,
We have discovered that it is possible to obtain a film-like ceramic that has a free shape depending on the shape of the conductive material used and is extremely thin, and has now completed the present invention.

That is, the present invention provides the following method for manufacturing membrane ceramics.

■ Forming an electrodeposition coating film containing ceramic raw materials on a conductive material using an electrodeposition paint containing ceramic raw materials, curing the coating film, peeling it off from the conductive material, and then firing it. A method for producing a characteristic film-like ceramic (hereinafter referred to as the first method of the present invention).

■ An electrodeposition coating containing a ceramic raw material is used to form an electrodeposition coating film containing a ceramic raw material on a conductive material, and after the coating film is cured, it is fired to coat the ceramic raw material on the conductive material. A method for producing a membrane-like ceramic (hereinafter referred to as the second invention method of the present application), characterized by forming a layer and then peeling the ceramic layer from a conductive material.

In the present invention, as the electrodeposition paint for adding the ceramic material, any known electrodeposition paint containing an anionic polymer resin or a cationic polymer resin as a resin component can be used.

Examples of anionic polymer resins in such electrodeposition paints include acrylic resins (including fatty acid-modified acrylic resins) having anionic groups such as carboxyl groups and sulfonic acid groups, alkyd resins, polyester resins, and maleated polybutadiene resins. etc. can be exemplified. As the cationic polymer resin, amino groups, quaternary ammonium bases,
Examples include acrylic resins and Epoquine resins having cationic groups such as quaternary phosphate groups. Among these resins, those that do not undergo rapid thermal decomposition particularly in the binder removal step are preferred. Particularly in the method of the first invention of the present application, resins that exhibit appropriate flexibility even after curing are preferred, such as polyester-modified epoxy resins, urethane-modified epoxy resins, etc., which are generally used for pre-coated metals. It can be used preferably. In addition to using a specially modified resin as described above, it is also possible to mix the electrodeposition resin component with another flexible water-soluble resin, such as an acrylic resin having a cationic group and a water-soluble urethane resin. It is also possible to use a mixture of prepolymers.

As ceramic raw materials, fine powders such as various oxides, carbides, nitrides, borides, hydroxides, etc. can be used, as in the production of ordinary ceramics, as well as several metal compounds such as metal soaps and metal alkoxides. can also be used. Oxides include alumina, titanium oxide, barium titanate,
Examples include ferrite, ittria, zirconia (including stabilized or partially stabilized zirconia), and mullite.

Examples of the carbide include silicon carbide, tungsten carbide, zirconium carbide, titanium carbide, and tantalum carbide.

Examples of the nitride include silicon nitride, boron nitride, aluminum nitride, zirconium nitride, and titanium nitride. Examples of the boride include aluminum boride, titanium boride, zirconium boride, tantalum boride, and tungsten boride. Examples of the hydroxide include aluminum hydroxide. Examples of metal soaps include zirconium salts, calcium salts, and yttrium salts of octylic acid, caproic acid, persatic acid, naphthenic acid, and the like. Examples of metal alkoxides include silicon tetraethoxide, zirconium tetraN-butoxide, titanium tetraisopropoxide, and aluminum triisopropoxide. In addition, if necessary, a glass powder such as borosilicate glass may be added to the above ceramic raw material as a fluxing agent component for the purpose of lowering the sintering temperature of the ceramic raw material.

In the present invention, first, the various ceramic raw materials described above are added to the electrodeposition paint, and by performing electrodeposition coating using the electrodeposition paint containing such ceramic raw materials, the electrodeposition containing the ceramic raw material is applied. A coating is formed on the conductive material. Among ceramic raw materials, those that are dispersed as powder in the electrodeposition paint are precipitated in the electrodeposition coating film as a powder, and liquid ceramics such as silicon tetraethoxide and titanium tetraisopropoxide Raw materials and ceramic raw materials that are soluble in the solvent of the electrodeposition paint, such as various salts of caproic acid with a small number of carbon atoms, are dispersed in the form of a colloid in the electrodeposition paint, but they are dispersed on the electrode surface during electrodeposition. It is insolubilized to form an electrodeposited coating film together with the resin component.

When using a ceramic raw material that is dispersed as a powder in the electrodeposition paint, it is preferable to use one having a particle size of about 5 μm or less. If a ceramic raw material powder with a diameter exceeding 5 μm is used, it is difficult to stably disperse and suspend it in the electrodeposition paint, and the uniformity and smoothness of the ceramic layer formed will be poor, which is not preferable. When alumina is used as a raw material, it is more preferably about 5 to 0.1 μm, and when itria-stabilized zirconia is used as a raw material, it is more preferably about 3 μm to 80 angstroms.

The appropriate concentration of the ceramic raw material in the electrodeposition paint is about 10 to 20% by weight.

The appropriate blending ratio of the resin component and the ceramic raw material in the electrodeposition paint is about 10 to 300 parts by weight, and 40 to 200 parts by weight of the resin to 100 parts by weight of the ceramic raw material.
It is preferable that it is about the same level. If the resin content is below this range,
The smoothness and uniformity of the electrocoated film formed by electrocoating deteriorates, and green molded bodies with poor flexibility are formed because the resin content is too low. It becomes difficult to peel off. On the other hand, if it exceeds this range, when the resulting green molded body is fired, the amount of components that are burned away will increase, making wrinkles and cracks more likely to occur, and the particles between the ceramic raw materials will not be sintered smoothly. This is not preferable because a uniform film-like ceramic cannot be obtained.

The electrodeposition paint used in the present invention may further contain neutralizing agents, organic solvents, surfactants, antifoaming agents, etc., which are used in ordinary electrodeposition paints, if necessary. The types and amounts of these additives may be the same as those for known electrodeposition coatings, and may be appropriately determined depending on the type of resin used.

Furthermore, if necessary, a crosslinking agent that is commonly included in conventional electrodeposition paints can also be blended. As a crosslinking agent,
For example, polyester resin with polyether chains introduced,
Known resins such as acrylic resins with high hydroxyl content, resol type phenolic resins, methylolated urea, melamine resins, polyamide resins such as water-soluble nylon, and blocked urethane prepolymers can be used, and the types of resins used can be used. It may be selected as appropriate.

The electrodeposition coating material containing the ceramic raw material used in the present invention can be obtained by dispersing or dissolving the above-mentioned components in water as a medium. The electrodeposition paint can be prepared by simply mixing the components, but by mechanically dispersing and dispersing them using a roll mill or ball mill, adsorption of the polymer resin to the ceramic raw material powder or fine powder of the ceramic raw material is possible. It is preferable to aim for

In the method of the present invention, a conductive material is immersed in an electrodeposition paint containing the ceramic raw material described above, and a voltage is applied using the conductive material as an electrode to deposit the ceramic raw material on the surface of the conductive material. Deposit a coating film.

As a conductive material, platinum 1. Metals such as gold, silver, copper, titanium, tantalum, molybdenum, manganese, iron, nickel, aluminum, alloys thereof, conductive metal compounds such as indium oxide, antimony oxide, tin oxide, carbon, graphite, etc. Various materials can be used. Furthermore, a composite conductive material in which a layer of metal, conductive metal compound, etc. is formed on an insulator such as glass, ceramics, or plastics can also be used. Such composite materials are
It can be obtained by a known method such as a swirl plating method, a sputtering method, a CVD method, a paste printing method, or a spray method. There are no particular restrictions on the shape of the conductive material in the present invention, and any shape can be used.

The electrodeposition coating method may be the same as the usual method generally practiced in the coating industry, depending on the type of resin used, and is generally applied at a liquid temperature of about 10 to 40°C and an applied voltage of 30 to 500°C. When an anionic polymer resin is used, the conductive material is used as the e-electrode, and when a cationic polymer resin is used, the conductive material is used as the e-electrode for electrodeposition. The time for electrodeposition coating may vary depending on the required amount of deposition, but is usually about 10 seconds to 3 minutes.

In the method of the present invention, a coating film is formed by an electrodeposition coating method, so it is not limited to a sheet-like molded product, and can easily be formed into various shapes such as a pipe shape and a concave shape depending on the shape of the conductive material. can get.

The thickness of the electrodeposition coating film is suitably about 15 to 150 μm. If it is less than 15 μm, the film thickness is too thin and a dense sintered body may not be obtained. On the other hand, if it exceeds 150 μm, the uniformity, smoothness, etc. of the electrodeposited film will be poor, and the film after sintering will be difficult to obtain. This is not preferable because the appearance of the shaped ceramic may become poor.

When forming an electrodeposition coating film by the method of the present invention, it is particularly preferable to use a sheet-shaped conductive material such as a metal tape and continuously forming the electrodeposition coating film while winding it up. By such a method, an electrodeposition coating film can be efficiently formed.

After forming an electrodeposited coating film containing a polymer resin and a ceramic raw material on a conductive material by the method described above, the resin component in the coating film is cured. The resin curing method may be the same as for ordinary electrodeposition coating, and depending on the type of resin, moisture and moisture can be removed by leaving it at room temperature or under heating of about 80 to 200°C for about 5 to 30 minutes. At the same time as the solvent evaporates, a crosslinking reaction of the resin component occurs, and the electrodeposited coating film is cured.

In the method of the first invention of the present application, after the resin component is cured, the electrodeposited coating film is peeled off from the conductive material to obtain a polymer resin molded body containing a ceramic raw material (hereinafter referred to as a green molded body).

The method for peeling off the green molded body is not particularly limited (various methods are possible. For example, as a physical method, using the difference in thermal expansion coefficient between the green molded body and the conductive material,
It can be peeled off by heat shock or heat cycles. Alternatively, as a mechanical method, a wedge-shaped object is driven between the green molded body and the conductive material to create a crevice, and the green molded body and the conductive material can then be peeled off by applying mechanical force and peeling. Furthermore, when using a conductive material that dissolves in acid, alkali, etc., a green molded body can also be obtained by dissolving only the conductive material by chemical dissolution treatment. The method of chemical dissolution is suitable for industrial production because of its good working efficiency. When using a chemical dissolution method, chemical dissolution is easy as a conductive material,
It is also preferable to use an inexpensive material; for example, aluminum, copper, iron, titanium, etc. can be suitably used. As the dissolving agent, aqueous solutions of alkali salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia, and acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid can be used. Hydrogen peroxide, persulfate, etc. can also be added as agents. The dissolving conditions such as the concentration of the dissolving agent and the temperature depend on the conductive material used.
It may be determined as appropriate.

According to the method of the first invention of the present application, by using an electrodeposition paint containing the above-mentioned polymer resin and ceramic raw material in a predetermined ratio, the green molded body formed has appropriate strength, flexibility, etc. It can be peeled off from the conductive material without causing damage such as cracking, and has a rating of 15 to 1.
It becomes possible to create a green molded body with an extremely thin film thickness of about 50 μm.

In a preferred embodiment of the method for producing a green molded body according to the method of the first invention of the present application, electrocoating is performed continuously while winding up a sheet-like conductive material such as a metal tape, and then electrocoating is performed. After the film is cured, the conductive material is cut into appropriate lengths, and the conductive material is dissolved by chemical dissolution treatment to obtain a green molded body. According to such a method, it becomes possible to continuously obtain green molded bodies, and work efficiency can be improved.

After obtaining the green molded body, the green molded body is heated while gradually increasing the temperature to decompose and remove organic compounds such as polymer resins in the green molded body (debinding process), and then the temperature is raised to the sintering temperature to produce the ceramic raw material. Sinter.

In the binder removal step, it is usually appropriate to raise the temperature at about 10 to 150 hr, preferably 150 hr.
-b In the heating process, if the temperature increase rate is too fast, the thermal decomposition of the organic matter will be insufficient, resulting in an increase in pores, and cracks and blisters caused by residual carbon during sintering.

Further, if the thermal decomposition is too rapid, wrinkles may appear on the surface, which is not preferable.

The decomposition of organic substances such as polymer resins is generally 300 to 600
Since the decomposition is carried out at a temperature of approximately 10°C, it may be maintained in this temperature range for approximately 10 minutes to 10 hours to ensure sufficient decomposition.

After the binder removal process is completed, the ceramic raw material is sintered by further heating to a high temperature to produce a membrane-like ceramic. The sintering temperature is the same as for conventional ceramic sheets.
It may be determined as appropriate depending on the type of raw material and the required sintered density. For example, when alumina is used as a raw material, 10
It is preferable to pre-fire at around 00°C and then sinter by raising the temperature to 1600°C or higher. In addition, when using zirconia as a raw material, it is pre-fired at around 1000°C and heated to 1500°C.
It is preferable to carry out sintering at a temperature elevated to .degree. C. or higher. In addition, when barium titanate is used as a raw material, 1050°
Dense ceramics can be obtained by sintering at a temperature of C or higher, preferably 1100°C or higher.

In the method of the second invention of the present application, an electrodeposited coating film containing a ceramic raw material is formed on a conductive material in the same manner as the method of the first invention of the present application, and after this is cured, heating is continued while gradually increasing the temperature. The organic compound in the coating film is decomposed and removed (debinding step), and then the temperature is raised to the sintering temperature of the ceramic raw material to sinter the ceramic raw material and form a ceramic layer on the conductive material.

The conditions for forming and curing the electrodeposited coating film in the method of the second invention of the present application may be the same as those of the method of the first invention of the present application, but the thickness of the ceramic layer obtained by sintering the electrodeposition coating film becomes too thin. Therefore, it is preferable that the thickness of the electrodeposition coating film is about 60 to 150 μm.

In addition, if the volumetric shrinkage of the ceramic layer caused by sintering is large, it will be difficult to obtain a uniform film-like ceramic, so it is preferable to use a relatively small amount of resin. It is appropriate that the resin content be approximately 10 to 40 parts by weight based on the weight of the resin.

In the method of the second invention of the present application, the ceramic is sintered with an electrodeposition coating film formed on the conductive material, so it is preferable that the conductive material has a melting point higher than the sintering temperature of the ceramic raw material used. For example, platinum, gold, silver, copper,
Depending on the ceramic raw material to be used, select the appropriate one from high melting point metals such as iron, nickel, titanium, tantalum, molybdenum, manganese, chromium, tungsten, cobalt, etc. or their alloys. It is appropriate to do so.

The binder removal and sintering of the ceramic raw material in the second invention method may be carried out under the same conditions as the binder removal and sintering of the green molded body in the first invention method, but the peeling of the ceramic layer after sintering may be avoided. Considering ease of use, in order to thin the diffusion layer between the ceramic layer and the conductive material, the sintering temperature may be lowered by about 50 to 100°C compared to the method of the first invention of the present application. preferable. For example, if alumina is used as a raw material, 1500
It is appropriate to perform the sintering at a temperature of about 1,550°C, and when using zirconia as a raw material, a temperature of 1,400 to 140°C is suitable.
It is appropriate to perform the sintering at about 50°C. In addition, if the sintered density of ceramics decreases by lowering the sintering temperature, increasing the sintering time will reduce the sintered density.
Sintered density can be improved.

In the method of the second invention of the present application, the ceramic raw material is sintered to form a ceramic layer on the conductive material, and then the ceramic layer is peeled off from the conductive material.
Obtain membranous ceramics.

As a method for peeling the ceramic layer from the conductive material, mechanical methods and physical methods similar to the method of the first invention of the present application are also possible, but when the ceramic layer and the conductive material are separated at the interface when sintering the ceramic, Since a diffusion layer may be formed and integrated, it is preferable to perform a chemical dissolution treatment to dissolve the conductive material and thereby peel off the ceramic layer. In the method of peeling by chemical dissolution treatment, the conductive material used is preferably a material that has heat resistance, is easy to undergo chemical dissolution treatment, and is inexpensive, such as iron, copper, nickel, titanium, molybdenum, etc. , manganese, chromium, tungsten, cobalt, etc., or alloys thereof can be suitably used. Specifically, depending on the type of conductive material used, the dissolving agent may include alkali salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid. An aqueous solution of an acid such as the above can be used, and if necessary, a dissolution accelerator such as hydrogen peroxide or persulfate can be added thereto. For example, when a molybdenum-manganese alloy, tungsten, or the like is used as the conductive material, an aqueous solution of a mineral acid such as hydrochloric acid, sulfuric acid, or nitric acid may be used.

The concentration of the aqueous solution of acid, alkali, etc. to be used may be appropriately determined within a range that does not adversely affect the ceramics, and it may be heated if necessary.

Effects of the Invention According to the method of the present invention, it is possible to easily obtain a membrane-shaped ceramic having a free shape depending on the shape of the conductive material used, without being limited to a sheet shape. In particular, according to the method of the first invention of the present application, a green molded body containing a large amount of resin component, having good flexibility and being easy to handle can be obtained. Furthermore, since a green molded body with a thin film thickness can be produced, a thin film ceramic having a thickness of about 10 μm can be produced as a final sintered body, and a ceramic having extremely high thermal conductivity can be obtained.

As described above, the present invention makes it possible to manufacture film-like ceramics with complex shapes and extremely thin film ceramics, and in the electronics field, it is possible to miniaturize and increase the density of laminated packages and printed laminated substrates. Can be done. Furthermore, these thin film ceramics are nearly transparent, and can be used as translucent ceramics for heat-resistant translucent porcelain such as window materials, jacket tubes for sodium lamps, transparent electrodes, and optical polarizing elements. Furthermore, as an ion-conductive thin film ceramic, it can be used as a sensor.
Alternatively, it can be expected to be used in the field of solid electrolyte applications.

Example Hereinafter, the present invention will be explained in more detail by showing examples.

Example 1 Y2O3 partially stabilized Zr02 with an average particle size of 0.1 μm (trademark: H8Y-3, OU, manufactured by Kigenso Kagaku Kogyo Co., Ltd.) 10
0 parts by weight, anionic polymer acrylic resin (contains melamine resin as a crosslinking agent, trademark: Honey Bright C-1,
A suspension was prepared by mixing and dispersing 250 parts by weight (solid content 50%, manufactured by Honey Kasei ■) and 750 parts by weight of water in a ball mill for 24 to 48 hours. After that, a clean 100 x 50
A 5US304 stainless steel plate was immersed in the suspension as a cathode, and heated at 100V for 1 minute and 30 seconds at a liquid temperature of 26°C.
Electricity was applied and electrodeposition painting was performed.

Next, the electrodeposited aluminum plate was taken out of the suspension, washed with water, pre-dried for 15 to 20 minutes at a temperature of around 80°C, and then further dried for 20 minutes at a temperature of 170 to 180°C.
The electrodeposited coating was cured by heat drying for 1 minute. Next, after peeling off the masking tape from the aluminum plate, 60
15 in a 10% sodium hydroxide solution heated to ~70°C.
It was immersed for ~20 minutes to completely dissolve the aluminum material and peel off the electrodeposition coating. After washing this well with water, drying it and punching it into 50 mm squares, two porous alumina plates (upper plate 50 x 50 x 3 mm; lower plate 50 x 50 x 10
mm), the temperature was raised to 500°C at 200°C per hour in a firing furnace, and the temperature was held at 500°C for 30 minutes to remove the binder. 1 at a speed of 600°C per hour.
The temperature was raised to 000 °C and held at 1000 °C for 30 minutes to perform pre-firing, then the temperature was raised to 1400 °C at 300 °C per hour and held at 1400 °C for 15 minutes to perform sintering.
A thin ceramic sheet of about 25 μm was obtained. The obtained ceramic sheet was in good condition with no cracks, etc., the firing shrinkage rate was about 45%, and no anisotropy was observed in the longitudinal and transverse directions.

Example 2 Partially stabilized Y2O3 Zr′0° with an average particle size of 0.1 μm (trademark: H8Y-3, OU, manufactured by Daiki Genso Kagaku Kogyo ■)
100 parts by weight, anionic polymer acrylic resin (trademark:
Honey Bright C-1, solid content 50%, produced by Honey Kasei ■) 250 parts, water-based flexible epoxy resin (trademark: Pararesin EP-1, solid content 50%, produced by Ohara Palladium Kagaku Kan Co., Ltd.) 1001ffffff 1 part, and A suspension was prepared by mixing and dispersing 750 parts of water in a ball mill for 24 hours. After that, clean and thoroughly degreased length 50mm x diameter 1
A 0 mm x 0.5 mm thick aluminum pipe (the inside was masked in advance with polyester masking tape) was used as an anode, and the entire cylindrical stainless steel container 110 mm in diameter x 120 mm deep containing the dispersion liquid was heated. As an anode, 200Vx at a liquid temperature of 20°C
Electricity was applied for 1 minute to perform electrodeposition coating. After that, Example 1
The obtained electrodeposition coating film was cured in the same manner as above. Next, after peeling off the internal masking tape, apply a 60 to 70
In a 10% sodium hydroxide solution warmed to ca.
The aluminum pipe material was immersed for 30 minutes to completely dissolve and the electrodeposited coating was peeled off. After washing this thing thoroughly with water,
It was dried and subjected to the same firing process as in Example 1 to produce a ceramic pipe with a film thickness of 50 μm.

Example 3 Alumina powder with an average particle size of 0.5 microns (trademark: UA-
5105, Showa Denko (m) 100 parts by weight, cationic epoxy water-soluble resin (trademark: Power Top U-700,
200 parts by weight (manufactured by Nippon Paint ■) and 500 parts by weight of water were mixed and dispersed in a ball mill for 24 hours to prepare a suspension. Next, a clean 50X50X0.2mm that has been thoroughly degreased.
A molybdenum plate (previously masked with polyester masking tape on one side) was used as a cathode, and a 100 x 50 x 1 piece of 5US304 stainless steel was used as an anode, and was immersed in the suspension.
Electricity was applied for 2 minutes at 0V to perform electrodeposition coating. Next, the electrocoated molybdenum plate was lifted out of the suspension, washed with water, and then
The electrodeposited coating film was cured by drying for 20 minutes at a temperature of 70 to 80°C, and then heat drying for 20 minutes at a temperature of 170 to 180°C. After peeling off the masking tape on one side, the molybdenum plate was placed on top of the zirconia plate with the electrodeposited side facing down, and the temperature was raised to 500℃ at 300℃ per hour in a firing furnace. 30
The binder was removed by holding for a minute. After that, every hour 5
Raise the temperature to 1000℃ at a rate of 00℃, and at 1000℃
Temporary firing is performed by holding for 0 minutes, followed by heating at 300°C per hour.
The temperature was raised to 1550° C. and held at 1550° C. for 15 minutes to sinter the alumina and form an alumina layer.

Next, this was added to 10-20% hydrochloric acid at 50-60°C for 20 minutes.
By dipping for ~30 minutes and melting the molybdenum plate, an alumina thin film ceramic sheet having a thickness of 50 μm was obtained.

(that's all)

Claims (2)

[Claims] (1) Using an electrodeposition paint containing ceramic raw materials,
A method for producing membrane ceramics, which comprises forming an electrodeposited coating film containing a ceramic raw material on a conductive material, curing the coating film, peeling it off from the conductive material, and then firing it. (2) Using an electrodeposition paint containing ceramic raw materials,
An electrodeposited coating film containing a ceramic raw material is formed on a conductive material, the coating film is cured, and then fired to form a ceramic layer on the conductive material. A method for producing membrane-like ceramics characterized by peeling from the membrane.